Electron emitter and its production method, cold-cathode field electron emitter and its production method, and cold-cathode filed electron emission displays and its production method

ABSTRACT

A cold cathode field emission device comprising a cathode electrode  11  formed on a supporting member  10,  a gate electrode  13  which is formed above the cathode electrode  11  and has an opening portion  14,  and an electron emitting portion  15  formed on a surface of a portion of the cathode electrode  11  which portion is positioned in a bottom portion of the opening portion  14,  said electron emitting portion  15  comprising a carbon-group-material layer  23,  and said carbon-group-material layer  23  being a layer formed from a hydrocarbon gas and a fluorine-containing hydrocarbon gas.

TECHNICAL FIELD

[0001] The present invention relates to an electron emitting apparatusfor emitting electrons from a carbon-group-material layer and amanufacturing method thereof, a cold cathode field emission devicehaving an electron emitting portion comprising a carbon-group-materiallayer and a manufacturing method thereof, and a cold cathode fieldemission display provided with such cold cathode field emission devicesand a manufacturing method thereof.

BACKGROUND ART

[0002] In the fields of displays for use in television receivers andinformation terminals, studies have been made for replacingconventionally mainstream cathode ray tubes (CRT) with flat-paneldisplays which are to comply with demands for a decrease in thickness, adecrease in weight, a larger screen and a high fineness. Such flat paneldisplays include a liquid crystal display (LCD), an electroluminescencedisplay (ELD), a plasma display panel (PDP) and a cold cathode fieldemission display (FED). Of these, a liquid crystal display is widelyused as a display for an information terminal. For applying the liquidcrystal display to a floor-type television receiver, however, it stillhas problems to be solved concerning a higher brightness and an increasein size. In contrast, a cold cathode field emission display uses coldcathode field emission devices (to be sometimes referred to as “fieldemission device” hereinafter) capable of emitting electrons from a solidinto a vacuum on the basis of a quantum tunnel effect without relying onthermal excitation, and it is of great interest from the viewpoints of ahigh brightness and a low power consumption.

[0003]FIGS. 20 and 21 shows a cold cathode field emission display towhich the field emission devices are applied (to be sometimes referredto as “display” hereinafter). FIG. 20 is a schematic partial end view ofthe display, and FIG. 21 is a schematic partial perspective view of thedisplay when a cathode panel CP and an anode panel AP are disassembled.

[0004] The field emission device shown in these drawings is a so-calledSpindt type field emission device having a conical electron emittingportion. Such a field emission device comprises a cathode electrode 111formed on a supporting member 110, an insulating layer 112 formed on thesupporting member 110 and the cathode electrode 111, a gate electrode113 formed on the insulating layer 112, an opening portion 114 formed inthe gate electrode 113 and the insulating layer 112, and a conicalelectron emitting portion 115 formed on the cathode electrode 111positioned in a bottom portion of the opening portion 114. Generally,the cathode electrode 111 and the gate electrode 113 are formed in theform of a stripe each in directions in which projection images of thesetwo electrodes cross each other at right angles. Generally, a pluralityof field emission devices are arranged in a region (corresponding to onepixel, and the region will be called an “overlapped region” or an“electron emitting region” hereinafter) where the projection images ofthe above two electrodes overlap. Further, generally, such electronemitting regions are arranged in the form of a matrix within aneffective field (which works as an actual display portion) of a cathodepanel CP.

[0005] An anode panel AP comprises a substrate 30, a phosphor layer 31(31R, 31B and 31G) which is formed on the substrate 30 and has apredetermined pattern, and an anode electrode 33 formed thereon. Onepixel is constituted of a group of the field emission devices formed inthe overlapped region of the cathode electrode 111 and the gateelectrode 113 on the cathode panel side and the phosphor layer 31 whichis opposed to the above group of the field emission devices and is onthe anode panel side. In the effective field, such pixels are arrangedon the order of hundreds of thousands to several millions. On thesubstrate 30 between one phosphor layer 31 and another phosphor layer31, a black matrix 32 is formed.

[0006] The anode panel AP and the cathode panel CP are arranged suchthat the electron emitting regions and the phosphor layers are opposedto each other, and the anode panel AP and the cathode panel CP arebonded to each other in their circumferential portions through a frame34, whereby the display is produced. In an ineffective field(ineffective field of the cathode panel CP in the example shown in thedrawings) which surrounds the effective field and where aperipheral-circuit for selecting pixels is formed, a through-hole 36 forvacuuming is provided, and a tip tube 37 is connected to thethrough-hole 36 and sealed after vacuuming. That is, a space surroundedby the anode panel AP, the cathode panel CP and the frame 34 is in avacuum state.

[0007] A relatively negative voltage is applied to the cathode electrode111 from an cathode-electrode control circuit 40, a relatively positivevoltage is applied to the gate electrode 113 from a gate-electrodecontrol circuit 41, and a positive voltage having a higher level thanthe voltage applied to the gate electrode 113 is applied to the anodeelectrode 33 from the anode-electrode control circuit 42. When such adisplay is used for displaying on its screen, a scanning signal isinputted to the cathode electrode 111 from the cathode-electrode controlcircuit 40, and a video signal is inputted to the gate electrode 113from the gate-electrode control circuit 41. Due to an electric fieldgenerated when a voltage is applied between the cathode electrode 111and the gate electrode 113, electrons are emitted from the electronemitting portion 115 on the basis of a quantum tunnel effect, and theelectrons are attracted toward the anode electrode 33 and collide withthe phosphor layer 31. As a result, the phosphor layer 31 is excited toemit light, and a desired image can be obtained. That is, the working ofthe display is controlled, in principle, by a voltage applied to thegate electrode 113 and a voltage applied to the electron emittingportion 115 through the cathode electrode 111.

[0008] In the above display constitution, it is effective to sharpen thetop end portion of the electron emitting portion for attaining a largecurrent of emitted electrons at a low driving voltage, and from thisviewpoint, the electron emitting portion 115 of the above Spindt typefield emission device can be said to have excellent performances.However, the formation of the conical electron emitting portion 115requires advanced processing techniques, and with an increase in thearea of the effective field, it is beginning to be difficult to form theelectron emitting portions 115 uniformly all over the effective fieldsince the number of the electron emitting portions 115 totals up to tensof millions in some cases.

[0009] There has been therefore proposed a so-called flat-surface typefield emission device which uses a flat electron emitting portionexposed in a bottom portion of an opening portion without using theconical electron emitting portion. The electron emitting portion of theflat-surface type field emission device is formed on a cathodeelectrode, and it is composed of a material having a lower work functionthan a material constituting the cathode electrode for achieving a highcurrent of emitted electrons even if the electron emitting portion isflat. In recent years, it has been proposed to use various types ofcarbon materials such as diamond-like carbon (DLC) as the abovematerial.

[0010] That is, for example, in Lecture No. 2p-H-6 on page 631 ofpreprints of No. 60 Applied Physics Society Lectures (1999), there isdisclosed a flat-surface-structured electron emitter obtained byscratch-processing a surface of a titanium thin film formed on a quartzsubstrate by an electron beam deposition method, with a diamond powder,then patterning the titanium thin film to form a several μm gap in acentral portion, and then, forming a non-doped diamond thin film on thetitanium thin film. In Lecture No. 2p-H-11 on page 632 of preprints ofNo. 60 Applied Physics Society Lectures (1999), there is disclosed amethod in which a carbon nano-tube is formed on a quartz glass providedwith a metal cross line.

[0011] The value of a voltage (threshold voltage) at which electronsbegin to be emitted from an electron emitting portion can be decreasesby usage of various carbon-containing materials including diamond-likecarbon. However, a gas or gaseous substance released from variousmembers constituting the cathode electrode and the display adheres to,or is adsorbed on, the electron emitting portion, and as a result, theelectron emitting portion is deteriorated in properties, which is known,for example, in the literature of MRS 2000 Spring Meeting, PreprintsQ1.3/R1.3, page 264 “SURFACE MODIFICATION OF Si FIELD EMITTER ARRAYS FORVACUUM SEALING”. The above literature reports that the formation of acarbon thin film on the surface of a silicon-based electron emittingportion can inhibit the adherence and adsorption of the gas or gaseoussubstance to/on the electron emitting portion.

[0012] However, the above literature does not suggest any means ofovercoming the problem of adherence and adsorption of a gas or gaseoussubstance to/on the electron emitting portion made from acarbon-containing material.

[0013] It is therefore an object of the present invention to provide anelectron emitting apparatus and a cold cathode field emission devicethat can overcome the problem that a gas or gaseous substance releasedfrom various members constituting, for example, a cold cathode fieldemission display adheres to, or is adsorbed on, an electron emittingportion to cause the electron emitting portion to deteriorate inproperties, manufacturing methods of these, and a cold cathode fieldemission display to which the above cold cathode field emission deviceis incorporated and a manufacturing method thereof.

DISCLOSURE OF THE INVENTION

[0014] An electron emitting apparatus according to a first aspect of thepresent invention for achieving the above object is constituted of anelectron emitting portion formed on an electrically conductive layer,the electron emitting portion comprising a carbon-group-material layer,and the carbon-group-material layer being a layer formed from ahydrocarbon gas and a fluorine-containing hydrocarbon gas.

[0015] In the electron emitting apparatus according to the first aspectof the present invention, preferably, a selective-growth region isformed between the electrically conductive layer and thecarbon-group-material layer, from the viewpoint that thecarbon-group-material layer is formed reliably in a predetermined regionof the electrically conductive layer and is not formed in an unnecessaryportion.

[0016] An electron emitting apparatus according to a second aspect ofthe present invention for achieving the above object is constituted ofan electron emitting portion formed on an electrically conductive layer,the electron emitting portion comprising a carbon-group-material layerand a fluoride-carbide-containing thin film formed on the surface of thecarbon-group-material layer, and the fluoride-carbide-containing thinfilm being a film formed from a fluorine-containing hydrocarbon gas.

[0017] An electron emitting apparatus according to a third aspect of thepresent invention for achieving the above object is constituted of anelectron emitting portion formed on an electrically conductive layer,

[0018] the electron emitting portion comprising a carbon-group-materiallayer, and

[0019] the carbon-group-material layer having a surface terminated(modified) with fluorine atoms.

[0020] In the electron emitting apparatus according to the third aspectof the present invention, preferably, the termination (modification) ofthe surface of the carbon-group-material layer with fluorine atoms iscarried out with a fluorine-containing hydrocarbon gas.

[0021] In the electron emitting apparatus according to the second orthird aspect of the present invention, there may be employed aconstitution in which the carbon-group-material layer is a layer formedfrom a hydrocarbon gas. The above constitution will be referred to as“electron emitting apparatus according to the second-A aspect of thepresent invention” or “electron emitting apparatus according to thethird-A aspect of the present invention” for convenience sake. In thesecases, preferably, a selective-growth region is formed between theelectrically conductive layer and the carbon-group-material layer, fromthe viewpoint that the carbon-group-material layer is formed reliably ina predetermined region of the electrically conductive layer and is notformed in an unnecessary portion.

[0022] Alternatively, in the electron emitting apparatus according tothe second or third aspect of the present invention, there may beemployed a constitution in which the carbon-group-material layer isformed of carbon-nano-tube structures. The above constitution will bereferred to as “electron emitting apparatus according to the second-Baspect of the present invention” or “electron emitting apparatusaccording to the third-B aspect of the present invention” forconvenience sake.

[0023] The cold cathode field emission device according to any one ofthe first to third aspects of the present invention for achieving theabove object is a cold cathode field emission device for constituting aso-called “two-electrodes” type cold cathode field emission display, andcomprises;

[0024] (a) a cathode electrode formed on a supporting member, and

[0025] (b) an electron emitting portion formed on the cathode electrode.

[0026] The cold cathode field emission device according to any one offourth to sixth aspects of the present invention is a cold cathode fieldemission device for constituting a so-called “three-electrodes” typecold cathode field emission, and comprises;

[0027] (a) a cathode electrode formed on a supporting member,

[0028] (b) a gate electrode which is formed above the cathode electrodeand has an opening portion, and

[0029] (c) an electron emitting portion formed in a portion of thecathode electrode which portion is positioned in a bottom portion of theopening portion.

[0030] In the cold cathode field emission device according to the firstor fourth aspect of the present invention, the electron emitting portioncomprises a carbon-group-material layer, and the carbon-group-materiallayer is a layer formed from a hydrocarbon gas and a fluorine-containinghydrocarbon gas.

[0031] Further, in the cold cathode field emission device according tothe second or fifth aspect of the present invention, the electronemitting portion comprises a carbon-group-material layer and afluoride-carbide-containing thin film formed on the surface of thecarbon-group-material layer, and the fluoride-carbide-containing thinfilm is a film formed from a fluorine-containing hydrocarbon gas.

[0032] In the cold cathode field emission device according to the thirdor sixth aspect of the present invention, the electron emitting portioncomprises a carbon-group-material layer, and the carbon-group-materiallayer has a surface terminated (modified) with fluorine atoms.

[0033] The cold cathode field emission display according to any one ofthe first to third aspects of the present invention is a so-called“two-electrodes” type cold cathode field emission display, and has aplurality of pixels,

[0034] each pixel being constituted of a cold cathode field emissiondevice, an anode electrode and a phosphor layer, said anode electrodeand said phosphor layer being formed on a substrate so as to face thecold cathode field emission device, and

[0035] the cold cathode field emission device comprising;

[0036] (a) a cathode electrode formed a supporting member, and

[0037] (b) an electron emitting portion formed on the cathode electrode.

[0038] The cold cathode field emission display according to any one ofthe fourth to sixth aspects of the present invention is a so-called“three-electrodes” type cold cathode field emission display, and has aplurality of pixels,

[0039] each pixel being constituted of a cold cathode field emissiondevice, an anode electrode and a phosphor layer, said anode electrodeand said phosphor layer being formed on a substrate so as to face thecold cathode field emission device, and

[0040] the cold cathode field emission device comprising;

[0041] (a) a cathode electrode formed on a supporting member,

[0042] (b) a gate electrode which is formed above the cathode electrodeand has an opening portion, and

[0043] (c) an electron emitting portion formed on a portion of thecathode electrode which portion is positioned in a bottom portion of theopening portion.

[0044] In the cold cathode field emission display according to the firstor fourth aspect of the present invention, the electron emitting portioncomprises a carbon-group-material layer, and the carbon-group-materiallayer is a layer formed from a hydrocarbon gas and a fluorine-containinghydrocarbon gas.

[0045] In the cold cathode field emission display according to thesecond or fifth aspect of the present invention, the electron emittingportion comprises a carbon-group-material layer and afluoride-carbide-containing thin film formed on the surface of thecarbon-group-material layer, and the fluoride-carbide-containing thinfilm is a film formed from a fluorine-containing hydrocarbon gas.

[0046] In the cold cathode field emission display according to the thirdor sixth aspect of the present invention, the electron emitting portioncomprises a carbon-group-material layer, and the carbon-group-materiallayer has a surface terminated (modified) with fluorine atoms.

[0047] In the cold cathode field emission devices according to the thirdand sixth aspects of the present invention, or in the cold cathode fieldemission displays according to the third and sixth aspects of thepresent invention, desirably, the termination (modification) of thesurface of the carbon-group-material layer with fluorine atoms iscarried out with a fluorine-containing hydrocarbon gas.

[0048] In the cold cathode field emission device according to any one ofthe second, third, fifth and sixth aspects of the present invention, orin the cold cathode field emission display according to any one of thesecond, third, fifth and sixth aspects of the present invention,desirably, the carbon-group-material layer is a layer formed from ahydrocarbon gas. The above constitution will be referred to as “coldcathode field emission device according to the second-A, third-A,fifth-A or sixth-A aspect of the present invention” or “cold cathodefield emission display according to the second-A, third-A, fifth-A orsixth-A aspect of the present invention” for convenience sake.

[0049] In the cold cathode field emission device according to any one ofthe second, third, fifth and sixth aspects of the present invention, orin the cold cathode field emission display according to any one of thesecond, third, fifth or sixth aspects of the present invention,desirably, the carbon-group-material layer is formed of carbon-nano-tubestructures. The above constitution will be referred to as “cold cathodefield emission device according to the second-B, third-B, fifth-B orsixth-B aspect of the present invention” or “the cold cathode fieldemission display according to the second-B, third-B, fifth-B or sixth-Baspect of the present invention” for convenience sake.

[0050] In the cold cathode field emission device according to any one ofthe first, second-A, third-A, fourth, fifth-A and sixth-A aspects of thepresent invention, or in the cold cathode field emission displayaccording to any one of the first, second-A, third-A, fourth, fifth-Aand sixth-A aspects of the present invention, desirably, aselective-growth region is formed between the cathode electrode and thecarbon-group-material layer, from the viewpoint that thecarbon-group-material layer is formed reliably in a predetermined regionof the cathode electrode and is not formed in an unnecessary portion.

[0051] In the cold cathode field emission device according to any one offourth to sixth aspects of the present invention, or in the cold cathodefield emission display according to any one of the fourth to sixthaspects of the present invention, it is desirable to employ aconstitution in which an insulating layer is formed on the supportingmember and the cathode electrode, and a second opening portioncommunicating with the opening portion (to be sometimes referred to as“first opening portion” for convenience sake hereinafter) made throughthe gate electrode is made through the insulating layer. However, thepresent invention shall not be limited to the above constitution, andthere may be employed a structure in which a metal layer (for example, asheet or striped-shape material made of a metal) constituting the gateelectrode having the first opening portion is spread and supported abovethe electron emitting portion through and with a gate electrodesupporting member.

[0052] The manufacturing method of an electron emitting apparatusaccording to a first aspect of the present invention for achieving theabove object comprises the step of forming an electron emitting portioncomprising a carbon-group-material layer, on an electrically conductivelayer, from a hydrocarbon gas and a fluorine-containing hydrocarbon gas.

[0053] The manufacturing method of an electron emitting apparatusaccording to a second aspect of the present invention for achieving thepresent invention comprises the steps of;

[0054] (A) forming a carbon-group-material layer on an electricallyconductive layer, and

[0055] (B) forming a fluoride-carbide-containing thin film on thesurface of the carbon-group-material layer from a fluorine-containinghydrocarbon gas, thereby to obtain an electron emitting portioncomprising the carbon-group-material layer and thefluoride-carbide-containing thin film formed on the surface of thecarbon-group-material layer.

[0056] The manufacturing method of an electron emitting apparatusaccording to a third aspect of the present invention for achieving thepresent invention comprises the steps of;

[0057] (A) forming a carbon-group-material layer on an electricallyconductive layer, and

[0058] (B) terminating (modifying) the surface of thecarbon-group-material layer with a fluorine-containing hydrocarbon gas,thereby to obtain an electron emitting portion comprising thecarbon-group-material layer whose surface is terminated (modified) withfluorine atoms.

[0059] In the manufacturing method of an electron emitting portionaccording to the second or third aspect of the present invention, thecarbon-group-material layer is preferably formed on the electricallyconductive layer from a hydrocarbon gas in the above step (A). The aboveconstitution will be referred to as “manufacturing method of an electronemitting apparatus according to the second-A aspect of the presentinvention” or “manufacturing method of an electron emitting apparatusaccording to the third-A aspect of the present invention” forconvenience sake.

[0060] Alternatively, in the manufacturing method of an electronemitting apparatus according to the second or third aspect of thepresent invention, it is preferred to employ a constitution in which adispersion of carbon-nano-tube structures in a binder material isapplied onto the electrically conductive layer and then the bindermaterial is fired or cured to form the carbon-group-material layer inthe step (A). More specifically, the carbon-nano-tube structures aredispersed in an organic binder material such as an epoxy resin oracrylic resin or in an inorganic binder material such as water glass,the resultant dispersion is, for example, applied onto a predeterminedregion of the electrically conductive layer, then, the solvent isremoved, and the binder material is fired or cured. As an applicationmethod, for example, a screen printing method can be employed. The aboveconstitution will be referred to as “manufacturing method of an electronemitting apparatus according to the second-B of the present invention”or “manufacturing method of an electron emitting apparatus according tothe third-B of the present invention” for convenience sake.

[0061] Alternatively, in the manufacturing method of an electronemitting apparatus according to the second or third aspect of thepresent invention, it is preferred to employ a constitution in which ametal compound solution in which the carbon-nano-tube structures aredispersed is applied onto the electrically conductive layer, and thenthe metal compound is fired, to form the carbon-group-material layer inthe above step (A). The above constitution will be referred to as“manufacturing method of an electron emitting apparatus according to thesecond-C aspect of the present invention” or “manufacturing method of anelectron emitting apparatus according to the third-C aspect of thepresent invention”.

[0062] In the manufacturing method of an electron emitting apparatusaccording to any one of the first, second-A and third-A aspects of thepresent invention, it is preferred to further provide the step offorming a selective-growth region on the electrically conductive layerbefore the formation of the carbon-group-material layer, from theviewpoint that the carbon-group-material layer is formed reliably in apredetermined of the electrically conductive layer and is not formed inan unnecessary portion.

[0063] The manufacturing method of a cold cathode field emission deviceaccording to a first aspect of the present invention for achieving theabove object is a manufacturing method of a cold cathode field emissiondevice for constituting a so-called “two-electrodes” type cold cathodefield emission display, and comprises the steps of;

[0064] (A) forming a cathode electrode on a supporting member, and

[0065] (B) forming an electron emitting portion on the cathodeelectrode,

[0066] in which the electron emitting portion comprises acarbon-group-material layer, and

[0067] the step of forming the electron emitting portion comprises thestep of forming the carbon-group-material layer from a hydrocarbon gasand a fluorine-containing hydrocarbon gas.

[0068] The manufacturing method of a cold cathode field emission displayaccording to a first aspect of the present invention for achieving theabove object is a manufacturing method of a so-called “two-electrodes”type cold cathode field emission display, in which a substrate having ananode electrode and a phosphor layer formed thereon and a supportingmember having a cold cathode field emission device formed thereon arearranged such that the phosphor layer and the cold cathode fieldemission device face each other, and the substrate and the supportingmember are bonded to each other in their circumferential portions, themethod including the steps of;

[0069] (A) forming a cathode electrode on the supporting member, and

[0070] (B) forming an electron emitting portion on the cathodeelectrode, thereby to form the cold cathode field emission device,

[0071] in which the electron emitting portion comprises acarbon-group-material layer, and

[0072] the step of forming the electron emitting portion comprises thestep of forming the carbon-group-material layer from a hydrocarbon gasand a fluorine-containing hydrocarbon gas.

[0073] In the manufacturing method of a cold cathode field emissiondevice according to the first aspect of the present invention, or in themanufacturing method of a cold cathode field emission display accordingto the first aspect of the present invention, preferably, interposedbetween the step (A) and the step (B) is the step of forming aselective-growth region on the cathode electrode, and the step (B) iscarried out by forming the electron emitting portion on theselective-growth region in place of forming the electron emittingportion on the cathode electrode, from the viewpoint that thecarbon-group-material layer is formed reliably in a predetermined regionof the cathode electrode and is not formed in an unnecessary portion.The above constitution will be referred to as “manufacturing method of acold cathode field emission device according to the first (1) aspect ofthe present invention” or “manufacturing method of a cold cathode fieldemission display according to the first (1) aspect of the presentinvention” for convenience sake.

[0074] The manufacturing method of a cold cathode field emission deviceaccording to a second aspect of the present invention for achieving theabove object is a manufacturing method of a cold cathode field emissiondevice for constituting a so-called “two-electrodes” type cold cathodefield emission display, and comprises the steps of;

[0075] (A) forming a cathode electrode on a supporting member,

[0076] (B) forming a carbon-group-material layer on the cathodeelectrode, and

[0077] (C) forming a fluoride-carbide-containing thin film on thesurface of the carbon-group-material layer from a fluorine-containinghydrocarbon gas, thereby to obtain an electron emitting portioncomprising the carbon-group-material layer and thefluoride-carbide-containing thin film formed on the surface of thecarbon-group-material layer.

[0078] The manufacturing method of a cold cathode field emission displayaccording to a second aspect of the present invention for achieving theabove object is a manufacturing method of a so-called “two-electrodes”type cold cathode field emission display, in which a substrate having ananode electrode and a phosphor layer formed thereon and a supportingmember having a cold cathode field emission device formed thereon arearranged such that the phosphor layer and the cold cathode fieldemission device face each other, and the substrate and the supportingmember are bonded to each other in their circumferential portions, themethod including the steps of;

[0079] (A) forming a cathode electrode on the supporting member,

[0080] (B) forming a carbon-group-material layer on the cathodeelectrode, and

[0081] (C) forming a fluoride-carbide-containing thin film on thesurface of the carbon-group-material layer from a fluorine-containinghydrocarbon gas, thereby to obtain an electron emitting portioncomprising the carbon-group-material layer and thefluoride-carbide-containing thin film formed on the surface of thecarbon-group-material layer, whereby the cold cathode field emissiondevice is formed.

[0082] The manufacturing method of a cold cathode field emission deviceaccording to a third aspect of the present invention for achieving theabove object is a manufacturing method of a cold cathode field emissiondevice for constituting a so-called “two-electrodes” type cold cathodefield emission display, and comprises the steps of;

[0083] (A) forming a cathode electrode on a supporting member,

[0084] (B) forming a carbon-group-material layer on the cathodeelectrode, and

[0085] (C) terminating (modifying) the surface of thecarbon-group-material layer with a fluorine-containing hydrocarbon gas,thereby to obtain an electron emitting portion comprising thecarbon-group-material layer having the surface terminated (modified)with fluorine atoms.

[0086] The manufacturing method of a cold cathode field emission displayaccording to a third aspect of the present invention for achieving theabove object is a manufacturing method of a so-called “two-electrodes”type cold cathode field emission display, in which a substrate having ananode electrode and a phosphor layer formed thereon and a supportingmember having a cold cathode field emission device formed thereon arearranged such that the phosphor layer and the cold cathode fieldemission device face each other, and the substrate and the supportingmember are bonded to each other in their circumferential portions, themethod including the steps of;

[0087] (A) forming a cathode electrode on the supporting member,

[0088] (B) forming a carbon-group-material layer on the cathodeelectrode, and

[0089] (C) terminating (modifying) the surface of thecarbon-group-material layer with a fluorine-containing hydrocarbon gas,thereby to obtain an electron emitting portion comprising thecarbon-group-material layer having the surface terminated (modified)with fluorine atoms, whereby the cold cathode field emission device isformed.

[0090] In the manufacturing method of a cold cathode field emissiondevice according to the second or third aspect of the present invention,or in the manufacturing method of a cold cathode field emission displayaccording to the second or third aspect of the present invention, it ispreferred to form the carbon-group-material layer on the cathodeelectrode from a hydrocarbon gas in the above step (B). The aboveconstitution will be referred to as “manufacturing method of a coldcathode field emission device according to the second-A or third-Aaspect of the present invention” or “manufacturing method of a coldcathode field emission display according to the second-A or third-Aaspect of the present invention” for convenience sake. In this case,preferably, interposed between the above steps (A) and (B) is the stepof forming a selective-growth region on the cathode electrode, and inthe above (B), the electron emitting portion is formed on theselective-growth region in place of forming the electron emittingportion on the cathode electrode, from the viewpoint that thecarbon-group-material layer is formed reliably in a predetermined regionof the cathode electrode and is not formed in an unnecessary portion.The above constitution will be referred to as “manufacturing method of acold cathode field emission device according to the second-A(1) aspector third-A(1) aspect of the present invention” or “manufacturing methodof a cold cathode field emission display according to the second-A(1)aspect or third-A(1) aspect of the present invention” for conveniencesake.

[0091] Alternatively, in the manufacturing method of a cold cathodefield emission device according to the second or third aspect of thepresent invention, in the manufacturing method of a cold cathode fieldemission device according to the fifth, sixth, eighth or ninth aspect ofthe present invention which will be described later, in themanufacturing method of a cold cathode field emission display accordingto the second or third aspect of the present invention, or in themanufacturing method of a cold cathode field emission display accordingto the fifth, sixth, eighth or ninth aspect of the present inventionwhich will be described later, there may be employed a constitution inwhich a dispersion of carbon nano-tube structures in a binder materialis applied onto the cathode electrode and the binder material is firedor cured to form the carbon-group-material layer in the step of formingthe electron emitting portion. More specifically, the carbon nano-tubestructures are dispersed in an organic binder material such as an epoxyresin or acrylic resin or in an inorganic binder material such as waterglass, the resultant dispersion is, for example, applied onto apredetermined region of the cathode electrode, and then the solvent isremoved and the binder material is fired or cured. As an applicationmethod, for example, a screen printing method can be employed.

[0092] The above constitution will be referred to as “manufacturingmethod of a cold cathode field emission device according to thesecond-B, third-B, fifth-B, sixth-B, eighth-B or ninth-B aspect of thepresent invention” or “manufacturing method of a cold cathode fieldemission display according to the second-B, third-B, fifth-B, sixth-B,eighth-B or ninth-B aspect of the present invention” for conveniencesake.

[0093] Alternatively, in the manufacturing method of a cold cathodefield emission device according to the second or third aspect of thepresent invention, in the manufacturing method of a cold cathode fieldemission device according to the fifth, sixth, eighth or ninth aspect ofthe present invention which will be described later, in themanufacturing method of a cold cathode field emission display accordingto the second or third aspect of the present invention, or in themanufacturing method of a cold cathode field emission display accordingto fifth, sixth, eighth or ninth aspect of the present invention whichwill be described later, there may be employed a constitution in which ametal compound solution in which the carbon nano-tube structures aredispersed is applied onto the cathode electrode and then the metalcompound is fired, to form the carbon-group-material layer in the stepof forming the electron emitting portion.

[0094] The above constitution will be referred to as “manufacturingmethod of a cold cathode field emission device according to thesecond-C, third-C, fifth-C, sixth-C, eighth-C or ninth-C aspect of thepresent invention” or “manufacturing method of a cold cathode fieldemission display according to the second-C, third-C, fifth-C, sixth-C,eighth-C or ninth-C aspect of the present invention” for conveniencesake.

[0095] The manufacturing method of a cold cathode field emission deviceaccording to any one of the fourth to sixth aspects of the presentinvention is a manufacturing method of a cold cathode field emissiondevice for constituting a so-called “three-electrodes” type cold cathodefield emission display, and comprises the steps of;

[0096] (A) forming a cathode electrode on a supporting member,

[0097] (B) forming an insulating layer on the supporting member and thecathode electrode,

[0098] (C) forming a gate electrode having an opening portion on theinsulating layer,

[0099] (D) forming a second opening portion through the insulatinglayer, said second opening portion communicating with the openingportion formed through the gate electrode, thereby to expose the cathodeelectrode in a bottom portion of the second opening portion, and

[0100] (E) forming an electron emitting portion on the cathode electrodeexposed in the bottom portion of the second opening portion.

[0101] The manufacturing method of a cold cathode field emission displayaccording to any one of the fourth to sixth aspects of the presentinvention for achieving the above object is a manufacturing method of aso-called “three-electrodes” type cold cathode field emission display,in which a substrate having an anode electrode and a phosphor layerformed thereon and a supporting member having a cold cathode fieldemission device formed thereon are arranged such that the phosphor layerand the cold cathode field emission device face each other, and thesubstrate and the supporting member are bonded to each other in theircircumferential portions, the method including the steps of;

[0102] (A) forming a cathode electrode on the supporting member,

[0103] (B) forming an insulating layer on the supporting member and thecathode electrode,

[0104] (C) forming a gate electrode having an opening portion on theinsulating layer,

[0105] (D) forming a second opening portion through the insulatinglayer, said second opening portion communicating with the openingportion formed through the gate electrode, thereby to expose the cathodeelectrode in a bottom portion of the second opening portion, and

[0106] (E) forming an electron emitting portion on the cathode electrodeexposed in the bottom portion of the second opening portion, whereby thecold cathode field emission device is formed.

[0107] Further, the manufacturing method of a cold cathode fieldemission device according to any one of the seventh to ninth aspects ofthe present invention for achieving the above object is a manufacturingmethod of a cold cathode field emission device for constituting aso-called “three-electrodes” type cold cathode field emission display,and comprises the steps of;

[0108] (A) forming a cathode electrode on a supporting member,

[0109] (B) forming an electron emitting portion on the cathodeelectrode, and

[0110] (C) forming a gate electrode having an opening portion above theelectron emitting portion.

[0111] The manufacturing method of a cold cathode field emission displayaccording to any one of the seventh to ninth aspects of the presentinvention for achieving the above object is a manufacturing method of aso-called “three-electrodes” type cold cathode field emission display,in which a substrate having an anode electrode and a phosphor layerformed thereon and a supporting member having a cold cathode fieldemission device formed thereon are arranged such that the phosphor layerand the cold cathode field emission device face each other, and thesubstrate and the supporting member are bonded to each other in theircircumferential portions, the method including the steps of;

[0112] (A) forming a cathode electrode on the supporting member,

[0113] (B) forming an electron emitting portion on the cathodeelectrode, and

[0114] (C) forming a gate electrode having an opening portion above theelectron emitting portion, whereby the cold cathode field emissiondevice is formed.

[0115] In the manufacturing method of a cold cathode field emissiondevice according to the fourth or seventh aspect of the presentinvention, or in the manufacturing method of a cold cathode fieldemission display according to fourth or seventh aspect of the presentinvention, the electron emitting portion comprises acarbon-group-material layer, and the step of forming the electronemitting portion comprises the step of forming the carbon-group-materiallayer from a hydrocarbon gas and a fluorine-containing hydrocarbon gas.

[0116] In the manufacturing method of a cold cathode field emissiondevice according to the fifth or eighth aspect of the present invention,or in the manufacturing method of a cold cathode field emission displayaccording to the fifth or eighth aspect of the present invention, theelectron emitting portion comprises a carbon-group-material layer and afluoride-carbide-containing thin film formed on the surface of thecarbon-group-material layer, and the step of forming the electronemitting portion comprises the step of forming thefluoride-carbide-containing thin film on the surface of the formedcarbon-group-material layer from a fluorine-containing hydrocarbon gas.

[0117] Further, in the manufacturing method of a cold cathode fieldemission device according to the sixth or ninth aspect of the presentinvention, or in the manufacturing method of a cold cathode fieldemission display according to the sixth or ninth aspect of the presentinvention, the electron emitting portion comprises acarbon-group-material layer, and the step of forming the electronemitting portion comprises the step of terminating (modifying) thesurface of the formed carbon-group-material layer with afluorine-containing hydrocarbon gas.

[0118] In the manufacturing method of an electron emitting apparatusaccording to the third aspect of the present invention, in themanufacturing method of a cold cathode field emission device accordingto any one of the third, sixth and ninth aspects of the presentinvention, or in the manufacturing method of a cold cathode fieldemission display according to any one of the third, sixth and ninthaspects of the present invention, the termination (modification) of thesurface of the carbon-group-material layer with fluorine atoms ispreferably carried out with a fluorine-containing hydrocarbon gas.

[0119] In the manufacturing method of a cold cathode field emissiondevice according to any one of the seventh to ninth aspects of thepresent invention, or in the manufacturing method of a cold cathodefield emission display according to any one of the seventh to ninthaspects of the present invention, there may be employed a constitutionin which

[0120] the step (B) is followed by forming an insulating layer on theentire surface, and

[0121] the step (C) is followed by forming a second opening portionthrough the insulating layer, said second opening portion communicatingwith the opening portion formed through the gate electrode, thereby toexpose the carbon-group-material layer in a bottom portion of the secondopening portion.

[0122] In the manufacturing method of a cold cathode field emissiondevice according to any one of the fifth, sixth, eighth and ninthaspects of the present invention, or in the manufacturing method of acold cathode field emission display according to any one of the fifth,sixth, eighth and ninth aspects of the present invention, preferably,the carbon-group-material layer is formed from a hydrocarbon gas in thestep of forming the electron emitting portion. The above constitutionwill be referred to as “manufacturing method of a cold cathode fieldemission device according to the fifth-A, sixth-A, eighth-A or ninth-Aaspect of the present invention” or “manufacturing method of a coldcathode field emission display according to the fifth-A, sixth-A,eighth-A or ninth-A aspect of the present invention” for conveniencesake.

[0123] Alternatively, in the manufacturing method of a cold cathodefield emission device according to any one of the fourth, fifth-A andsixth-A aspects of the present invention, or in the manufacturing methodof a cold cathode field emission display according to any one of thefourth, fifth-A and sixth-A aspects of the present invention, there maybe also employed a constitution in which

[0124] interposed between the step (A) and the step (B) is the step offorming a selective-growth region on the cathode electrode,

[0125] an insulating layer is formed on the supporting member, theselective-growth region and the cathode electrode in the step (B),

[0126] a second opening portion is formed through the insulating layerin the step (D), said second opening portion communicating with theopening portion formed through the gate electrode, thereby to expose theselective-growth region in the bottom portion of the second openingportion, and

[0127] the electron emitting portion is formed on the selective-growthregion exposed in the bottom portion of the second opening portion inthe step (E).

[0128] The above constitution will be referred to as “manufacturingmethod of a cold cathode field emission device according to the fourth(1), fifth-A(1) or sixth-A(1) aspect of the present invention” or“manufacturing method of a cold cathode field emission display accordingto the fourth (1), fifth-A(1) or sixth-A(1) aspect of the presentinvention” for convenience sake.

[0129] Alternatively, in the manufacturing method of a cold cathodefield emission device according to any one of the fourth, fifth-A andsixth-A aspects of the present invention, or in the manufacturing methodof a cold cathode field emission display according to any one of thefourth, fifth-A and sixth-A aspects of the present invention, there maybe employed a constitution in which

[0130] interposed between the step (D) and the step (E) is the step offorming a selective-growth region on the cathode electrode exposed inthe bottom portion of the second opening portion, and

[0131] the electron emitting portion is formed on the selective-growthregion in the step (E) in place of forming the electron emitting portionon the cathode electrode exposed in the bottom portion of the secondopening portion.

[0132] The above constitution will be referred to as “manufacturingmethod of a cold cathode field emission device according to the fourth(2), fifth-A(2) or sixth-A(2) aspect of the present invention” or“manufacturing method of a cold cathode field emission display accordingto the fourth (2), fifth-A(2) or sixth-A(2) aspect of the presentinvention” for convenience sake.

[0133] In the manufacturing method of a cold cathode field emissiondevice according to any one of the seventh, eighth-A and ninth-A aspectsof the present invention, or in the manufacturing method of a coldcathode field emission display according to any one of the seventh,eighth-A and ninth-A aspects of the present invention, there may beemployed a constitution in which

[0134] interposed between the step (A) and the step (B) is the step offorming a selective-growth region on the cathode electrode, and

[0135] the electron emitting portion is formed on the selective-growthregion in the step (B) in place of forming the electron emitting portionon the cathode electrode.

[0136] The above constitution will be referred to as “manufacturingmethod of a cold cathode field emission device according to the seventh(1), eighth-A(1) or ninth-A(1) aspect of the present invention” or“manufacturing method of a cold cathode field emission display accordingto the seventh (1), eighth-A(1) or ninth-A(1) aspect of the presentinvention” for convenience sake.

[0137] In the electron emitting apparatus or in the manufacturing methodthereof in the present invention, in the cold cathode field emissiondevice or in the manufacturing method thereof in the present invention,and in the cold cathode field emission display or in the manufacturingmethod thereof in the present invention, including embodiments accordingto various aspects of the present invention (all of these will besometimes generally referred to as “the present invention”), thehydrocarbon gas as a raw material for forming the carbon-group-materiallayer includes hydrocarbon gases such as methane (CH₄), ethane (C₂H₆),propane (C₃H₈), butane (C₄H₁₀), ethylene (C₂H₄), acetylene (C₂H₂),mixtures of these gases, and mixtures of these hydrocarbon gases withhydrogen gas. Further, there may be used a gas prepared by gasifyingmethanol, ethanol, acetone, benzene, toluene, xylene or the like, ormixtures of these gasified gases with hydrogen. Further, for stabilizingdischarging and for promoting plasma dissociation, a rare gas such ashelium (He), argon (Ar) or the like may be introduced.

[0138] The fluorine-containing hydrocarbon gas is selected fromperfluorocarbons. Specifically, the fluorine-containing hydrocarbon gasincludes saturated fluorine-containing hydrocarbon gases such as CF₄gas, C₂F₆ gas and C₃F₈ gas, and unsaturated fluorine-containinghydrocarbon gases such as C₃F₄ gas and C₄F₈ gas. Further, hydrogen- andfluorine-containing hydrocarbon gases may be used, and specific examplesthereof include CH₃F gas and CH₂F₂ gas. Generally, with an increase inthe content of a fluorine component constituting the fluorine-containinghydrocarbon gas, the deposition of a fluoride-carbide-containing thinfilm (CF_(x) thin film) from the fluorine-containing hydrocarbon gascomes to be more difficult. That is, for forming afluoride-carbide-containing thin film, it is preferred to use afluorine-containing hydrocarbon gas whose fluorine component contentconstituting the fluorine-containing hydrocarbon gas is small. Forterminating (modifying) the surface of the carbon-group-material layerwith fluorine atoms, it is preferred to use a fluorine-containinghydrocarbon gas whose fluorine component content constituting thefluorine-containing hydrocarbon gas is large.

[0139] In the present invention, the carbon-group-material layer can beconstituted from a graphite thin film, an amorphous carbon thin film, adiamond-like carbon thin film, a fullerene thin film, carbon nano-tubesor carbon-nano-fibers. When the carbon-group-material layer is formedfrom a hydrocarbon gas, the method of forming the carbon-group-materiallayer includes CVD methods such as a microwave plasma method, atransformer-coupled plasma method, an inductively coupled plasma method,an electron cyclotron resonance plasma method, an RF plasma method, ahelicon wave plasma CVD method and a capacitively coupled plasma CVDmethod, and a CVD method using a diode parallel plate plasma enhancedCVD system. The form of the thus-formed carbon-group-material layer notonly includes the form of a thin film and a plate but also includes acarbon whisker, a carbon nano-tube and a carbon nano-fiber.Specifically, the above form includes nano-crystal diamond, nano-crystalgraphite, a carbon nano-tube, a carbon nano-fiber and a carbon sheet.Under some forming conditions, the thus-formed carbon-group-materiallayer has the form of a cone.

[0140] Specifically, the carbon nano-tube structure includes a carbonnano-tube and a carbon nano-fiber. More specifically, theelectron-emitting portion may be constituted of carbon nano-tubes, itmay be constituted of carbon nano-fibers, or it may be constituted of amixture of carbon nano-tubes with carbon nano-fibers. Macroscopically,the carbon nano-tube and carbon nano-fiber may have the form of a powderor a thin film. The carbon nano-tube structure constituted of the carbonnano-tube and carbon nano-fiber can be produced or formed by a known PVDmethod as an arc discharge method and a laser abrasion method; and anyone of various CVD methods such as a plasma CVD method, a laser CVDmethod, a thermal CVD method, a gaseous phase synthetic method and agaseous phase growth method.

[0141] In the manufacturing method of an electron emitting apparatusaccording to any one of the second-C and third-C aspects of the presentinvention, the manufacturing method of a cold cathode field emissiondevice according to any one of the second-C, third-C, fifth-C, sixth-C,eighth-C and ninth-C aspects of the present invention, and themanufacturing method of a cold cathode field emission display accordingto any one of the second-C, third-C, fifth-C, sixth-C, eighth-C andninth-C aspects of the present invention, the carbon nano-tubestructures are fixed to the surface of the cathode electrode or theelectrically conductive layer with a matrix containing metal atomsderived from the metal compound. The matrix is preferably constituted ofan electrically conductive metal oxide. More specifically, it ispreferably constituted of tin oxide, indium oxide, indium-tin oxide,zinc oxide, antimony oxide or antimony-tin oxide. After the firing,there can be obtained a state where part of each carbon nano-tubestructure is embedded in the matrix, or there can be obtained a statewhere the entire portion of each carbon nano-tube is embedded in thematrix. The matrix preferably has a volume resistivity of 1×10⁻⁹ Ω·m to5×10⁻⁶ Ω·m.

[0142] The metal compound for constituting the metal compound solutionincludes, for example, an organometal compound, an organic acid metalcompound and metal salts (for example, chloride, nitrate and acetate).The organic acid metal compound solution is, for example, a solutionprepared by dissolving an organic tin compound, an organic indiumcompound, an organic zinc compound or an organic antimony compound in anacid (for example, hydrochloric acid, nitric acid or sulfuric acid) anddiluting the resultant solution with an organic solvent (for example,toluene, butyl acetate or isopropyl alcohol). Further, the organic metalcompound solution is, for example, a solution prepared by dissolving anorganic tin compound, an organic indium compound, an organic zinccompound or an organic antimony compound in an organic solvent (forexample, toluene, butyl acetate or isopropyl alcohol). When the amountof the solution is 100 parts by weight, the solution preferably has acomposition containing 0.001 to 20 parts by weight of the carbonnano-tube structures and 0.1 to 10 parts by weight of the metalcompound. The solution may contain a dispersing agent and a surfactant.From the viewpoint of increasing the thickness of the matrix, anadditive such as carbon black or the like may be added to the metalcompound solution. In some cases, the organic solvent may be replacedwith water.

[0143] The method for applying, onto the cathode electrode or theelectrically conductive layer, the metal compound solution in which thecarbon nano-tube structures are dispersed includes a spray method, aspin coating method, a dipping method, a die quarter method and a screenprinting method. Of these, a spray method is preferred in view ofeasiness in application.

[0144] There may be employed a constitution in which the metal compoundsolution in which the carbon nano-tube structures are dispersed isapplied onto the cathode electrode or the electrically conductive layer,the metal compound solution is dried to form a metal compound layer,then, an unnecessary portion of the metal compound layer on the cathodeelectrode or the electrically conductive layer is removed, and then themetal compound is fired. Otherwise, an unnecessary portion of the metalcompound layer on the cathode electrode or the electrically conductivelayer may be removed after the metal compound is fired. Otherwise, themetal compound solution may be applied only onto a desired region of thecathode electrode or the electrically conductive layer.

[0145] The temperature for firing the metal compound is preferably, forexample, a temperature at which the metal salt is oxidized to form ametal oxide having electric conductivity, or a temperature at which theorganometal compound or an organic acid metal compound is decomposed toform a matrix (for example, a metal oxide having electric conductivity)containing metal atoms constituting the organometal compound or theorganic acid metal compound. For example, the above temperature ispreferably at least 300° C. The upper limit of the firing temperaturecan be a temperature at which elements constituting the electronemitting apparatus, the field emission device or the cathode panel donot suffer any thermal damage and the like.

[0146] In the manufacturing method of an electron emitting apparatusaccording to any one of the second-B, third-B, second-C and third-Caspects of the present invention, in the manufacturing method of an coldcathode field emission device according to any one of the second-B,third-B, fifth-B, sixth-B, eighth-B and ninth-B aspects of the presentinvention, in the manufacturing method of an cold cathode field emissiondisplay according to any one of the second-B, third-B, fifth-B, sixth-B,eighth-B and ninth-B aspects of the present invention, in themanufacturing method of an cold cathode field emission device accordingto any one of the second-C, third-C, fifth-C, sixth-C, eighth-C andninth-C aspects of the present invention, and in the manufacturingmethod of an cold cathode field emission display according to any one ofthe second-C, third-C, fifth-C, sixth-C, eighth-C and ninth-C aspects ofthe present invention, it is preferred to carry out a kind of anactivation treatment (washing treatment) of the surface of thecarbon-group-material layer after the forming of thecarbon-group-material layer, since the efficiency of emission ofelectrons from the electron-emitting portion is further improved. Theabove activation treatment includes a plasma treatment in an atmospherecontaining a gas such as hydrogen gas, ammonia gas, helium gas, argongas, neon gas, methane gas, ethylene gas, acetylene gas or nitrogen gas.

[0147] In the electron emitting apparatus according to any one of thefirst to third aspects of the present invention in which theselective-growth region is formed, in the cold cathode field emissiondevice according to any one of the first to sixth aspects of the presentinvention in which the selective-growth region is formed, and in thecold cathode field emission display according to any one of the first tosixth aspects of the present invention in which the selective-growthregion is formed, desirably, the selective-growth region is formed in amanner in which metal particles adhere onto the surface of theelectrically conductive layer or the cathode electrode or in which ametal thin film or an organometal compound thin film is formed on thesurface of the electrically conductive layer or the cathode electrode.

[0148] In the cold cathode field emission device according to any one ofthe fourth to sixth aspects of the present invention in which theselective-growth region is formed, and in the cold cathode fieldemission display according to any one of the fourth to sixth aspects ofthe present invention in which the selective-growth region is formed,the selective-growth region may be formed in that portion of the cathodeelectrode which is positioned in a bottom portion of the openingportion, or the selective-growth region may be also formed so as toextend from that portion of the cathode electrode which is positioned ina bottom portion of the opening portion to a surface of that portion ofthe cathode electrode which is different from the cathode electrodeportion in the bottom portion of the opening portion. Further, theselective-growth region may be formed on the entire surface or part ofthe surface of that portion of the cathode electrode that is positionedin the bottom portion of the opening portion.

[0149] In the manufacturing method of an cold cathode field emissiondevice according to any one of the fourth (2), fifth-A(2) and sixth-A(2)aspects of the present invention, and in the manufacturing method of ancold cathode field emission display according to any one of the fourth(2), fifth-A(2) and sixth-A(2) aspects of the present invention, thestep of forming a selective-growth region on the surface of the cathodeelectrode (to be referred to as “the step of forming theselective-growth region” hereinafter) can be the step of forming a masklayer on the cathode electrode in a state where the surface of thecathode electrode is exposed in a central portion of the bottom portionof the second opening portion (i.e., forming a mask layer at least on aside wall of the second opening portion), and then allowing metalparticles to adhere onto, or forming a metal thin layer or anorganometallic compound thin layer on, the mask layer and the exposedsurface of the cathode electrode.

[0150] The above mask layer can be formed, for example, by a method inwhich a resist material layer or a hard mask material layer is formed onthe entire surface and making a hole in a portion of the resist materiallayer or the hard mask material layer which portion is positioned in thecentral portion of the bottom portion of the second opening portion bylithography. In a state where the mask layer covers part of the cathodeelectrode which part is positioned in the bottom portion of the secondopening portion, the side wall of the second opening portion, the sidewall of the first opening portion, the insulating layer and the gateelectrode, the selective-growth region is formed on the surface of thecathode electrode which surface is positioned in the central portion ofthe bottom portion of the second opening portion. Therefore,short-circuiting between the cathode electrode and the gate electrodethrough the metal particles or the metal thin layer can be reliablyprevented. In some cases, the mask layer may cover the gate electrodealone. Otherwise, the mask layer may cover only the gate electrode inthe vicinity of the first opening portion, or the mask layer may coverthe gate electrode in the vicinity of the first opening portion and theside walls of the first and second opening portions. In these cases, acarbon-group-material layer may be formed on the gate electrodedepending upon an electrically conductive material constituting the gateelectrode. However, electrons are not emitted when the abovecarbon-group-material layer is not placed in a high-intensity electricfield. It is preferred to remove the mask layer before the formation ofthe carbon-group-material layer on the selective-growth region.

[0151] The step of forming the selective-growth region preferablycomprises the step of allowing metal particles to adhere onto, orforming a metal thin film or an organometal compound thin film on, theportion of the cathode electrode where the selective-growth region is tobe formed, thereby to obtain the selective-growth region formed byallowing metal particles to adhere onto, or forming a metal thin film oran organometal compound thin film on, the surface of the portion of thecathode electrode.

[0152] Otherwise, for making more reliable the selective-growth of thecarbon-group-material layer on the selective-growth region, after themetal particles are allowed to adhere onto, or the metal thin layer orthe organometallic compound thin layer is formed on, the surface of thecathode electrode, it is preferred to remove a metal oxide (so-callednatural oxide film) on the surface of each metal particle or on thesurface of the metal thin layer or the organometallic compound thinlayer. The metal oxide on the surface of each metal particle or on thesurface of the metal thin layer or the organometallic compound thinlayer is preferably removed, for example, by plasma reduction treatmentbased on, in a hydrogen gas atmosphere, a microwave plasma method, atransformer-coupled plasma method, an inductively coupled plasma method,an electron cyclotron resonance plasma method or an RF plasma method; bysputtering in an argon gas atmosphere; or by washing, for example, withan acid such as hydrofluoric acid or a base. Preferably, the step ofremoving the metal oxide on the surface of each metal particle or on thesurface of the metal thin layer or the organometallic compound thinlayer is carried out immediately before the formation of thecarbon-group-material layer on the selective-growth region. In theproduction of the electron emitting apparatus of the present invention,further, the above-explained various steps can be applied to the portionof the electrically conductive layer in which portion theselective-growth region is to be formed. “The portion of theelectrically conductive layer in which portion the selective-growthregion is to be formed” will be sometimes simply referred to as“electrically conductive layer portion”, and “the portion of the cathodeelectrode in which portion the selective-growth region is to be formed”will be sometimes simply referred to as “cathode electrode portion”,hereinafter.

[0153] The method for allowing the metal particles to adhere onto thesurface of the electrically conductive layer portion or the cathodeelectrode portion includes, for example, a method in which, in a statewhere a region other than the region where the selective-growth regionis to be formed in the electrically conductive layer or the cathodeelectrode is covered with a proper material (for example, a mask layer),a layer composed of a solvent and the metal particles is formed on thesurface of the electrically conductive layer portion or the cathodeelectrode portion, and then, the solvent is removed while retaining themetal particles. Alternatively, the step of allowing the metal particlesto adhere onto the surface of the electrically conductive layer portionor the cathode electrode portion includes, for example, a method inwhich, in a state where a region other than the region where theselective-growth region is to be formed in the electrically conductivelayer or the cathode electrode is covered with a proper material (forexample, a mask layer), metal compound particles containing metal atomsconstituting the metal particles are allowed to adhere onto the surfaceof the electrically conductive layer or the cathode electrode, and thenthe metal compound. particles are heated to decompose them, wherebythere is obtained the selective-growth region constituted of the portionof the electrically conductive layer or the cathode electrode whichportion has the surface onto which the metal particles adhere. In theabove method, specifically, a layer composed of a solvent and metalcompound particles is formed on the electrically conductive layerportion or the cathode electrode portion, and the solvent is removedwhile retaining the metal compound particles. The above metal compoundparticles are preferably composed of at least one material selected fromthe group consisting of halides (for example, iodides, chlorides,bromides, etc.), oxides and hydroxides of the metal and organic metalfor constituting the metal particles.. In the above methods, thematerial (for example, mask layer) covering the region other than theregion where the selective-growth region is to be formed in theelectrically conductive layer or the cathode electrode is removed at aproper stage.

[0154] Although differing depending upon materials for constituting themetal thin layer, the method for forming the metal thin layer on theelectrically conductive layer portion or the cathode electrode portionis selected, for example, from a plating method such as anelectroplating method and an electroless plating method, a chemicalvapor deposition method (CVD method) including an MOCVD method, aphysical vapor deposition method (PVD method) and a method of pyrolyzingan organometallic compound, in a state where a region other than theregion where the selective-growth region is to be formed in theelectrically conductive layer or the cathode electrode is covered with aproper material. The physical vapor deposition method includes (a)vacuum deposition methods such as an electron beam heating method, aresistance heating method and a flash deposition method, (b) a plasmadeposition method, (c) sputtering methods such as a bipolar sputteringmethod, a DC sputtering method, a DC magnetron sputtering method, ahigh-frequency sputtering method, a magnetron sputtering method, an ionbeam sputtering method and a bias sputtering method, and (d) ion platingmethods such as a DC (direct current) method, an RF method, amulti-cathode method, an activating reaction method, an electric fielddeposition method, a high-frequency ion plating method and a reactiveion-plating method.

[0155] Preferably, the metal particles or the metal thin layer forforming the selective-growth region are/is composed of at least onemetal selected from the group consisting of molybdenum (Mo), nickel(Ni), titanium (Ti), chromium (Cr), cobalt (Co), tungsten (W), zirconium(Zr), tantalum (Ta), iron (Fe), copper (Cu), platinum (Pt), zinc (Zn),cadmium (Cd), germanium (Ge), tin (Sn), lead (Pb), bismuth (Bi), silver(Ag), gold (Au), indium (In) and thallium (Tl).

[0156] The organometallic compound thin layer constituting theselective-growth region can be formed from an organometallic compoundcontaining at least one element selected from the group consisting ofzinc (Zn), tin (Sn), aluminum (Al), lead (Pb), nickel (Ni) and cobalt(Co). Further, it is preferably composed of a complex compound. Examplesof the ligand constituting the above complex compound includeacetylacetone, hexafluoroacetylacetone, dipivaloylmethane andcyclopentadienyl. The organometallic compound thin layer may containpart of a decomposition product from an organometallic compound.

[0157] The step of forming the organometallic compound thin layer on theelectrically conductive layer portion or the cathode electrode portioncan be the step of forming a layer composed of an organometalliccompound solution on the electrically conductive layer portion or thecathode electrode portion, or the step of sublimating an organometalliccompound to deposit it on the electrically conductive layer portion orthe cathode electrode portion. In these cases, the organometalliccompound thin layer constituting the selective-growth region ispreferably composed of an organometallic compound containing at leastone element selected from the group consisting of zinc (Zn), tin (Sn),aluminum (Al), lead (Pb), nickel (Ni) and cobalt (Co). Further, it ispreferably composed of a complex compound. Examples of the ligandconstituting the above complex compound include acetylacetone,hexafluoroacetylacetone, dipivaloylmethane and cyclopentadienyl. Theorganometallic compound thin layer may contain part of a decompositionproduct from an organometallic compound.

[0158] In the manufacturing method of a cold cathode field emissiondevice according to any one of the fourth to ninth aspects of thepresent invention, or in the manufacturing method of a cold cathodefield emission display according to any one of the fourth to ninthaspects of the present invention, the method of forming a gate electrodehaving a first opening portion on the insulating layer includes, forexample, a method in which an electrically conductive material layer forconstituting the gate electrode is formed on the insulating layer; then,a patterned first mask material layer is formed on the electricallyconductive material layer; the electrically conductive material layer isetched with using the above first mask material layer as an etchingmask, to pattern the electrically conductive material layer; the firstmask material layer is removed; then, a patterned second mask materiallayer is formed on the electrically conductive material layer and theinsulating layer; and the electrically conductive material layer isetched with using the above second mask material layer as an etchingmask, to form the first opening portion. Alternatively, there may beemployed a method in which the gate electrode having the first openingportion is directly formed by a screen printing method. In these cases,the method of forming the second opening portion, communicating with thefirst opening portion formed through the gate electrode, in theinsulating layer can be a method in which the insulating layer is etchedwith using the second mask material layer as an etching mask, or can bea method in which the insulating layer is etched with using the firstopening portion formed through the gate electrode as an etching mask.The first opening portion and the second opening portion have therelationship of a one-to-one correspondence. That is, one second openingportion is formed for one first opening portion.

[0159] In the manufacturing method of a cold cathode field emissiondevice according to any one of the seventh to ninth aspects of thepresent invention, or in the manufacturing method of a cold cathodefield emission display according to any one of the seventh to ninthaspects of the present invention, the step of forming the gate electrodehaving the opening portion above the carbon-group-material layer or thestep of forming the gate electrode having the opening portion above theselective-growth region may comprise the steps of forming astripe-shaped gate electrode supporting member composed of an insulatingmaterial on the supporting member and arranging the gate electrodecomposed of a stripe-shaped or sheet-shaped metal layer having aplurality of opening portions formed therein, above thecarbon-group-material layer or the selective-growth region such that themetal layer is in contact with top surfaces of the gate electrodesupporting members.

[0160] When the cold cathode field emission display is so-called“three-electrodes” type, generally, the cathode electrode has an outerform of a stripe, and the gate electrode also has an outer form of astripe. The cathode electrode in the form of a stripe extends in onedirection, and the gate electrode in the form of a stripe extends inanother direction. Preferably, a projection image of the cathodeelectrode in the form of a stripe and a projection image of the gateelectrode in the form of a stripe cross each other at right angles. In aregion where projection images of these two electrodes overlap (theregion corresponding to one pixel and being an electron emitting regionwhere the cathode electrode and the gate electrode overlap), oneselective-growth region or a plurality of selective-growth regions arepositioned. In the effective field of the cathode panel (a region whichworks as an actual display portion), further, such electron emittingregions are arranged in the form of a two-dimensional matrix.

[0161] When the cold cathode field emission display is of a so-called“two-electrodes” type, the cathode electrode has the outer form of astripe, and the anode electrode also has the outer form of a stripe.Alternatively, the cathode electrode has an outer so as to correspond toone pixel, and the anode electrode is shaped in the form of one sheetcovering an effective field.

[0162] The plan form of the first or second opening portion (formobtained by cutting the first or second opening portion with animaginary plane in parallel with the cathode electrode) may be any formsuch as a circle, an oval, a rectangle, a polygon, a rounded rectangleor a rounded polygon. As described above, the first opening portion canbe formed, for example, by isotropic etching or by a combination ofanisotropic etching and isotropic etching. The first opening portion canbe directly formed depending upon the forming method of the gateelectrode. The second opening portion can also be formed, for example,by isotropic etching or by a combination of anisotropic etching andisotropic etching.

[0163] It is sufficient that the carbon-group-material layer should beformed on the surface of the portion of the cathode electrode whichportion is positioned in the bottom portion of the second openingportion. The carbon-group-material layer may be formed so as to extendfrom the portion of the cathode electrode which portion is positioned inthe bottom portion of the second opening portion to a surface of aportion of the cathode electrode which portion is located in other thanthe bottom portion of the second opening portion. Further, thecarbon-group-material layer may be formed on the entirety of the surfaceof the portion of the cathode electrode which portion is positioned inthe bottom portion of the second opening portion, or it may be formed inpart of the above portion.

[0164] In the present invention, there may be employed a constitution inwhich the electrically conductive layer or the cathode electrode isconstituted of one layer of an electrically conductive material layer oris constituted of a three layers of a lower electrically conductivematerial layer, a resistance layer formed on the lower electricallyconductive material layer, and an upper electrically conductive materiallayer formed on the resistance layer. In the latter case, theselective-growth region is formed on the upper electrically conductivematerial layer. When the resistance layer is formed, uniformelectron-emitting properties of the electron emitting portions can beattained. The material for constituting a resistance layer includescarbon-containing materials such as silicon carbide (SiC) and SiCN; SiN;semiconductor materials such as amorphous silicon and the like; andrefractory metal oxides such as ruthenium oxide (RuO₂), tantalum oxideand tantalum nitride. The resistance layer can be formed by a sputteringmethod, a CVD method or a screen-printing method. The resistance valueof the resistance layer is approximately 1×10⁵ to 1×10⁷ Ω, preferablyseveral MΩ.

[0165] When the cold cathode field emission display is a so-called“three-electrodes” type, there may be employed a constitution in which asecond insulating layer is further formed on the gate electrode and theinsulating layer and a focus electrode is formed on the secondinsulating layer. Otherwise, the focus electrode may be formed above thegate electrode. The above focus electrode is provided for converging thepass of electrons which are emitted through the opening portion andattracted toward the anode electrode so that the brightness can beimproved and that an optical crosstalk among neighboring pixels can beprevented. The focus electrode is effective particularly for a so-calledhigh-voltage type cold cathode field emission display in which the anodeelectrode and the cathode electrode have a potential difference on theorder of several kilovolts and have a relatively large distance from oneto the other. A relatively negative voltage is applied to the focuselectrode from a focus-electrode control circuit. It is not necessarilyrequired to provide the focus electrode per cold cathode field emissiondevice. For example, the focus electrode may be extended in apredetermined direction in which the cold cathode field emission devicesare arranged, so that a common focusing effect can be exerted on aplurality of the cold cathode field emission devices.

[0166] In the manufacturing method of a cold cathode field emissiondisplay according to any one of the first to ninth aspects of thepresent invention, the bonding of the substrate and the supportingmember in their circumferential portions may be carried out with anadhesive layer or with a frame made of an insulating rigid material suchas glass or ceramic and an adhesive layer. When the frame and theadhesive layer are used in combination, the facing distance between thesubstrate and the supporting member can be adjusted to be longer byproperly determining the height of the frame than that obtained when theadhesive layer alone is used. While a frit glass is generally used as amaterial for the adhesive layer, a so-called low-melting-point metalmaterial having a melting point of approximately 120 to 400° C. may beused. The low-melting-point metal material includes In (indium; meltingpoint 157° C.); an indium-gold low-melting-point alloy; tin(Sn)-containing high-temperature solders such as Sn₈₀Ag₂₀ (melting point220 to 370° C.) and Sn₉₅Cu₅ (melting point 227 to 370° C.); lead(Pb)-containing high-temperature solders such as Pb_(97.5)Ag_(2.5)(melting point 304° C.), Pb_(94.5)Ag_(5.5) (melting point 304-365° C.)and Pb_(97.5)Ag_(1.5)Sn_(1.0) (melting point 309° C.); zinc(Zn)-containing high-temperature solders such as Zn₉₅Al₅ (melting point380° C.); tin-lead-containing standard solders such as Sn₅Pb₉₅ (meltingpoint 300-314° C.) and Sn₂Pb₉₈ (melting point 316-322° C.); and brazingmaterials such as Au₈₈Gal₂ (melting point 381° C.) (all of the aboveparenthesized values show atomic %).

[0167] When three members of the substrate, the supporting member andthe frame are bonded, these three members may be bonded at the sametime, or one of the substrate and the supporting member may be bonded tothe frame at a first stage and then the other of the substrate and thesupporting member may be bonded to the frame at a second stage. Whenbonding of the three members or bonding at the second stage is carriedout in a high-vacuum atmosphere, a space surrounded by the substrate,the supporting member, the frame and the adhesive layer comes to be avacuum space upon bonding. Otherwise, after the three members arebonded, the space surrounded by the substrate, the supporting member andthe frame may be vacuumed to obtain a vacuum space. When the vacuumingis carried out after the bonding, the pressure in an atmosphere duringthe bonding may be any one of atmospheric pressure and reduced pressure,and the gas constituting the atmosphere may be ambient atmosphere or aninert gas containing nitrogen gas or a gas (for example, Ar gas) comingunder the group O of the periodic table.

[0168] When the vacuuming is carried out after the bonding, thevacuuming can be carried out through a tip tube pre-connected to thesubstrate and/or the supporting member. Typically, the tip tube isformed of a glass tube and is bonded to a circumference of athrough-hole formed in an ineffective field of the substrate and/or thesupporting member (i.e., a field other than the effective field whichworks as a display portion) with a frit glass or the abovelow-melting-point metal material. After the space reaches apredetermined vacuum degree, the tip tube is sealed by thermal fusion.It is preferred to heat and then temperature-decrease the cold cathodefield emission display as a whole before the sealing, since residual gascan be released into the space, and the residual gas can be removed outof the space by vacuuming.

[0169] The supporting member for constituting the cathode electrode maybe any supporting member so long as it has a surface constituted of aninsulating member. The supporting member includes a glass substrate, aglass substrate having an insulating film formed on its surface, aquartz substrate, a quartz substrate having an insulating film formed onits surface and a semiconductor substrate having an insulating filmformed on its surface. From the viewpoint that the production cost isdecreased, it is preferred to use a glass substrate or a glass substratehaving an insulating film formed on its surface. Examples of the glasssubstrate include high-distortion glass, soda glass (Na₂O·CaO·SiO₂),borosilicate glass (Na₂O·B₂O₃·SiO₂), forsterite (2MgO·SiO₂) and leadglass (Na₂O·PbO·SiO₂). The substrate for constituting the anode panelcan have the same constitution as that of the above supporting member.In the electron emitting apparatus of the present invention, it isrequired to form the electrically conductive layer on the supportingmember. Such a supporting member can be selected from the insulatingmaterials or the same supporting members that are used for constitutingthe above cathode panel.

[0170] In the electron emitting apparatus according to any one of thefirst, second-A and third-A aspects of the present invention, in thecold cathode field emission device and the manufacturing method thereofaccording to any one of the first, second-A, third-A, fourth, fifth-Aand sixth-A aspects of the present invention, in the cold cathode fieldemission display and the manufacturing method thereof according to anyone of the first, second-A, third-A, fourth, fifth-A and sixth-A aspectsof the present invention, or in the manufacturing method of a coldcathode field emission device or in a cold cathode field emissiondisplay according to any one of the seventh, eighth-A and ninth-Aaspects of the present invention, it is preferred to constitute theelectrically conductive layer or the cathode electrode from copper (Cu),silver (Ag) or gold (Au), from the viewpoint that the resistance of theelectrically conductive layer or the cathode electrode is decreased andthat the carbon-group-material layer is reliably formed from ahydrocarbon gas without forming the selective-growth region.

[0171] When the selective-growth region is provided or thecarbon-group-material layer is constituted of carbon-nano tubestructure, the material for constituting an electrically conductivelayer and a cathode electrode can be selected from metals such astungsten (W), niobium (Nb), tantalum (Ta), titanium (Ti), molybdenum(Mo), chromium (Cr), aluminum (Al), copper (Cu), gold (Au), silver (Ag)and the like; alloys and compounds containing these metal elements (forexample, nitrides such as TiN and suicides such as WSi₂, MoSi₂, TiSi₂and TaSi₂); semiconductors such as silicon (Si); carbon thin film suchas diamond; and indium-tin oxide (ITO). Although not specially limited,the thickness of the cathode electrode is approximately 0.05 to 0.5 μm,preferably 0.1 to 0.3 μm.

[0172] The material for constituting the gate electrode includes atleast one metal selected from the group consisting of tungsten (W),niobium (Nb), tantalum (Ta), titanium (Ti), molybdenum (Mo), chromium(Cr), aluminum (Al), copper (Cu), gold (Au), silver (Ag), nickel (Ni),cobalt (Co), zirconium (Zr), iron (Fe), platinum (Pt) and zinc (Zn);alloys or compounds containing these metal elements (for example,nitrides such as TiN and silicides such as WSi₂, MoSi₂, TiSi₂ andTaSi₂); semiconductors such as silicon (Si); and electrically conductivemetal oxides such as ITO (indium-tin oxide), indium oxide and zincoxide.

[0173] The method for forming the cathode electrode and the gateelectrode includes a combination of deposition methods such as anelectron beam deposition method, a hot filament deposition method, asputtering method, a CVD method or an ion plating method with an etchingmethod; a screen-printing method; a plating method; and a lift-offmethod. When a screen-printing method or a plating method is employed,the cathode electrodes and the gate electrodes in the form of stripescan be directly formed.

[0174] As a material for constituting an insulating layer and a secondinsulating layer, SiO₂-containing material such as SiO₂, BPSG, PSG, BSG,AsSG, PbSG, SiON and spin on glass (SOG), low melting-point glass and aglass paste, SiN, an insulating resin such as polyimide and the like canbe used alone or in combination. The insulating layer and the secondinsulating layer can be formed by a known method such as a CVD method,an application method, a sputtering method or a screen printing method.

[0175] The material for the anode electrode can be selected dependingupon the constitution of the cold cathode field emission display. Whenthe cold cathode field emission display is a transmission type (thesubstrate corresponds to a display portion) and when the anode electrodeand the phosphor layer are stacked on the substrate in this order, notonly the substrate on which the anode electrode is formed but also theanode electrode itself are required to be transparent, and a transparentelectrically conductive material such as ITO (indium-tin oxide) is used.When the cold cathode field emission display is a reflection type (thesupporting member corresponds to a display portion), or when the coldcathode field emission is a transmission type but when the phosphorlayer and the anode electrode are stacked on the substrate in this order(the anode electrode works as a metal back film as well), not only ITOcan be used, but also the material can be selected from those materialswhich are discussed with regard to the cathode electrode, the gateelectrode and the focus electrode, and preferably, can be selected fromaluminum (Al) or chromium (Cr). When the anode electrode is constitutedof aluminum (Al) or chromium (Cr), the specific thickness of the anodeelectrode is 3×10⁻⁸ m (30 nm) to 1.5×10⁻⁷ m (150 nm), preferably 5×10⁻⁸m (50 nm) to 1×10⁻⁷ m (100 nm). The anode electrode can be formed by avapor deposition method or a sputtering method.

[0176] The phosphor material for the phosphor layer can be selected froma fast-electron-excitation type phosphor material or aslow-electron-excitation type phosphor material. When the cold cathodefield emission display is a monochrome display, it is not required topattern the phosphor layer. When the cold cathode field emission displayis a color display, preferably, the phosphor layers corresponding tothree primary colors of red (R), green (G) and blue (B) patterned in theform of stripes or dots are alternately arranged. A black matrix may befilled in a gap between one patterned phosphor layer and anotherphosphor layer for improving a display screen in contrast.

[0177] Examples of the constitution of the anode electrode and thephosphor layer include (1) a constitution in which the anode electrodeis formed on the substrate and the phosphor layer is formed on the anodeelectrode and (2) a constitution in which the phosphor layer is formedon the substrate and the anode electrode is formed on the phosphorlayer. In the above constitution (1), a so-called metal back film may beformed on the phosphor layer. In the above constitution (2), the metalback layer may be formed on the anode electrode.

[0178] Further, the anode panel is preferably provided with a pluralityof ribs for preventing the occurrence of a so-called optical crosstalk(color mixing) that is caused when electrons recoiling from the phosphorlayer or secondary electrons emitted from the phosphor layer enteranother phosphor layer, or for preventing the collision of electronswith other phosphor layer when electrons recoiling from the phosphorlayer or secondary electrons emitted from the phosphor layer enter otherphosphor layer over the rib.

[0179] The form of the ribs includes the form of a lattice (grilles),that is, a form in which the rib corresponding to one pixel surroundsthe phosphor layer having a plan form of a nearly rectangle (ordot-shaped), and a stripe or band-like form that extends in parallelwith opposite two sides of a rectangular or stripe-shaped phosphorlayer. When the rib(s) have the form of a lattice, the rib may have aform in which the rib continuously or discontinuously surrounds foursides of one phosphor layer. When the rib(s) has the form of a stripe,the stripe may be continuous or discontinuous. The formed ribs may bepolished to flatten the top surface of each rib.

[0180] For improving the contrast of display images, preferably, a blackmatrix that absorbs light from the phosphor layer is formed between onephosphor layer and another adjacent phosphor layer and between the riband the substrate. As a material for constituting the black matrix, itis preferred to select a material that absorbs at least 99% of lightfrom the phosphor layer. The above material includes carbon, a thinmetal film (made, for example, of chromium, nickel, aluminum, molybdenumand an alloy of these), a metal oxide (for example, chromium oxide),metal nitride (for example, chromium nitride), a heat-resistant organicresin, a glass paste, and a glass paste containing a black pigment orelectrically conductive particles of silver or the like. Specificexamples thereof include a photosensitive polyimide resin, chromiumoxide and a chromium oxide/chromium stacked film. Concerning thechromium oxide/chromium stacked film, the chromium film is to be incontact with the substrate.

[0181] The electron emitting apparatus of the present invention can benot only applied to the electron emitting portion of a cold cathodefield emission device but also incorporated into various electron beamsources typified by an electron beam source in an electron gunincorporated into a cathode ray tube, and a fluorescence display tube.

[0182] In the electron emitting apparatus according to any one of thefirst to third aspects of the present invention, in the cold cathodefield emission device according to any one of the first to third aspectsof the present invention, or in the cold cathode field emission displayaccording to any one of the first to third aspects of the presentinvention, it is sufficient to bring the carbon-group-material layer ina proper electric field (for example, an electric field having anintensity of about 10⁷ volt/m) for allowing the carbon-group-materiallayer to emit electrons. In the cold cathode field emission device or inthe cold cathode field emission display according to any one of thefourth to sixth aspects of the present invention, electrons are emittedfrom the electron emitting portion comprising the carbon-group-materiallayer on the basis of an electric field (for example, an electric fieldhaving an intensity of about 10⁷ volt/m) caused by applying voltages tothe cathode electrode and the gate electrode. And, these electronscollide with the phosphor layer to give an image.

[0183] In the present invention, the carbon-group-material layer isformed from a hydrocarbon gas and a fluorine-containing hydrocarbon gas,or the fluoride-carbide-containing thin film is formed on the surface ofthe carbon-group-material layer, or the surface of thecarbon-group-material layer is terminated (modified) with fluorineatoms. Therefore, the electron emitting portion exhibits a kind of waterrepellency, and the adherence or adsorption of a gas or gaseoussubstance released from various members constituting the cathodeelectrode or the cold cathode field emission display, particularly,water to/on the electron emitting portion (specifically, thecarbon-group-material layer) can be inhibited. As a result, thedeterioration of properties of the electron emitting portion can beprevented. Further, since the electron emitting portion comprises thecarbon-group-material layer, there can be obtained a cold cathode fieldemission device having high electron emission efficiency.

[0184] In the present invention, further, when the electron emittingportion comprising the carbon-group-material layer is formed on theselective-growth region, a kind of catalytic reaction on the surface ofthe selective-growth region can be counted on. As a result, nucleationat an initial growth stage of the carbon-group-material layer smoothlyproceeds, and the nucleation promotes the growth of thecarbon-group-material layer that follows, so that the electron emittingportion comprising the carbon-group-material layer can be formed on thepredetermined portion of the electrically conductive layer or thecathode electrode. Further, it is not required to carry out thepatterning of the carbon-group-material layer for bringing thecarbon-group-material layer into a predetermined form. Furthermore, whenthe electron emitting portion comprising the carbon-group-material layeris formed on that portion of the cathode electrode which is positionedin the bottom portion of the opening portion and is constituted of amaterial having a function as a kind of catalyst, it is not required tocarry out the patterning of the carbon-group-material layer for bringingthe carbon-group-material layer into a predetermined form. Moreover,when the electron emitting portion is constituted of thecarbon-nano-tube structures, the electron emitting portion can be easilyformed.

BRIEF DESCRIPTION OF THE DRAWINGS

[0185]FIG. 1 is a schematic partial cross-sectional view of a coldcathode field emission display of Example 1.

[0186]FIG. 2 is a schematic perspective view of one electron emittingregion in the cold cathode field emission display of Example 1.

[0187]FIGS. 3A to 3D are schematic partial cross-sectional views of asupporting member, etc., for explaining the manufacturing method of anelectron emitting apparatus of Example 1.

[0188]FIGS. 4A to 4D are schematic partial cross-sectional views of asubstrate, etc., for explaining the manufacturing method of an anodepanel in the cold cathode field emission display of Example 1.

[0189]FIG. 5 is a schematic partial cross-sectional view of an electronemitting apparatus of Example 2.

[0190]FIGS. 6A and 6B are schematic partial cross-sectional views of asupporting member, etc., for explaining the manufacturing method of anelectron emitting apparatus of Example 4.

[0191]FIG. 7 is a schematic partial end view of a cold cathode fieldemission display of Example 5.

[0192]FIGS. 8A and 8B are schematic partial end views of the supportingmember, etc., for explaining the manufacturing method of a cold cathodefield emission device of Example 5.

[0193]FIG. 9 is a schematic partial end view of a cold cathode fieldemission display of Example 8.

[0194]FIGS. 10A to 10C are schematic partial end views of a supportingmember, etc., for explaining the manufacturing method of a cold cathodefield emission device of Example 8.

[0195]FIGS. 11A and 11B, following FIG. 10C, are schematic partial endviews of the supporting member, etc., for explaining the manufacturingmethod of the cold cathode field emission device of Example 8.

[0196]FIGS. 12A and 12B, following FIG. 11BC, are schematic partial endviews of the supporting member, etc., for explaining the manufacturingmethod of the cold cathode field emission device of Example 8.

[0197]FIGS. 13A and 13B are schematic partial end views of a supportingmember, etc., for explaining a cold cathode field emission device ofExample 11.

[0198]FIGS. 14A and 14B are schematic partial end views of a supportingmember, etc., for explaining a cold cathode field emission device ofExample 17.

[0199]FIG. 15, following FIG. 14B, is a schematic partial end view ofthe supporting member, etc., for explaining the cold cathode fieldemission device of Example 17.

[0200]FIG. 16 is a schematic partial end view of a supporting member,etc., for explaining a cold cathode field emission device of Example 18.

[0201]FIGS. 17A and 17B are schematic partial end views of a supportingmember, etc., for explaining a cold cathode field emission device ofExample 19 or 20.

[0202]FIGS. 18A and 18B, following FIG. 17B, are schematic partial endviews of a supporting member, etc., for explaining the cold cathodefield emission device of Example 19 or 20.

[0203]FIG. 19 is a schematic partial end view of a cold cathode fieldemission device having a focus electrode in the present invention.

[0204]FIG. 20 is a schematic partial end view of a conventional coldcathode field emission display having a Spindt type cold cathode fieldemission device.

[0205]FIG. 21 is a schematic partial perspective view of a cold cathodefield emission display when a cathode panel and an anode panel areseparated.

BEST MODE FOR CARRYING OUT THE INVENTION

[0206] The present invention will be explained on the basis of Exampleswith reference to drawings.

EXAMPLE 1

[0207] Example 1 is concerned with the electron emitting apparatusaccording to the first aspect of the present invention and themanufacturing method thereof, the cold cathode field emission device (tobe called “field emission device” for short hereinafter) according tothe first aspect of the present invention, the cold cathode fieldemission display (to be called “display” for short hereinafter)according to the first aspect, the manufacturing method of a fieldemission device according to the first aspect (more specifically, first(1) aspect), and the manufacturing method of a display according to thefirst aspect (more specifically, first (1) aspect). Incidentally,displays in Examples 1 to 4 are so-called “two-electrodes” typedisplays.

[0208]FIG. 1 shows a schematic partial cross-sectional view of thedisplay of Example 1, FIG. 2 shows a schematic perspective view of onefield emission device or one electron emitting apparatus, and FIG. 3Dshows a schematic partial cross-sectional view of one field emissiondevice or one electron emitting apparatus.

[0209] The electron emitting apparatus or field emission device inExample 1 comprises a cathode electrode (electrically conductive layer)11 having a selective-growth region 20 formed on its surface, and anelectron emitting portion 15 comprising a carbon-group-material layer 23formed on the selective-growth region 20. The selective-growth region 20is constituted of metal particles 21 adhering to the surface of thecathode electrode (electrically conductive layer) 11. Further, thecarbon-group-material layer 23 is a layer formed from a hydrocarbon gas(specifically, CH₄) and a fluorine-containing hydrocarbon gas(specifically, CF₄).

[0210] The display of Example 1 has a cathode panel CP having aneffective field where a large number of the above electron emittingapparatus or the field emission devices are formed in the form of atwo-dimensional matrix and an anode panel AP, and the display has aplurality of pixels. The cathode panel CP and the anode panel AP arebonded to each other through a frame 34 in their circumferentialportions. Further, the cathode panel CP has a vacuuming through-hole(not shown) in its ineffective field, and a tip tube (not shown) whichis to be sealed after vacuuming is connected to the through-hole. Theframe 34 is made of ceramic or glass and has a height, for example, of1.0 mm. In some cases, an adhesive layer alone may be used in place ofthe frame 34.

[0211] The anode panel AP comprises a substrate 30, a phosphor layer 31formed on the substrate 30 and formed in a predetermined pattern and ananode electrode 33 composed, for example, of one sheet-shaped aluminumthin film covering the entire surface of the effective field. A blackmatrix 32 is formed on the substrate 30 between one phosphor layer 31and another phosphor layer 31. The black matrix 32 may be omitted. Whenit is intended to produce a monochrome display, the phosphor layer 31 isnot required to be in a predetermined pattern. Further, an anodeelectrode composed of a transparent electrically conductive film of ITOor the like may be formed between the substrate 30 and the phosphorlayer 31. Otherwise, the anode panel AP may be constituted of the anodeelectrode 33 composed of a transparent electrically conductive filmprovided on the substrate 30, the phosphor layer 31 and the black matrix32 both formed on the anode electrode 32, and a light reflectionelectrically conductive film which is composed of aluminum, is formed onthe phosphor layer 31 and the black matrix 32 and is electricallyconnected to the anode electrode 33.

[0212] Each pixel is constituted of the cathode electrode 11 having arectangular form, the electron emitting portion 15 formed thereon andthe phosphor layer 31 arranged in the effective field of the anode panelAP so as to face the electron emitting apparatus or the field emissiondevice. In the effective field, such pixels are arranged on the order,for example, of hundreds of thousands to several millions.

[0213] Further, spacers 35 as auxiliary means are disposed between thecathode panel CP and the anode panel AP for maintaining a constantdistance between these two panels, and the spacers 35 are disposed inregular intervals in the effective field. The form of the spacers 35 isnot limited to a columnar form, and the spacers 35 may have a sphericalform or may be ribs in the form of a stripe. It is not required toarrange the spacers 35 in four corners of each overlap region of theanode electrode and the cathode electrode. The spacers 35 may be moresparsely arranged, or the arrangement thereof may be irregular.

[0214] In the display, the voltage to be applied to the cathodeelectrode 11 is controlled in the unit of one pixel. When viewed as aplan view, the cathode electrode 11 has a nearly rectangular form as isschematically shown in FIG. 2, and each cathode electrode 11 isconnected to a cathode-electrode control circuit 40A through a wiring11A and a switching element (not shown) formed, for example, of a TFT ora transistor. Further, the anode electrode 33 is connected to ananode-electrode control circuit 42. When a voltage higher than athreshold voltage is applied to each cathode electrode 11, electrons areemitted from the electron emitting portion 15 on the basis of a quantumtunnel effect due to an electric field generated by the anode electrode33, and the electrons are attracted toward the anode electrode 33 andcollide with the phosphor layer 31. The brightness is controlled on thebasis of a voltage applied to the cathode electrode 11.

[0215] The manufacturing method of the electron emitting apparatus, thefield emission device and the display in Example 1 will be explainedwith reference to FIGS. 3A to 3D and FIGS. 4A to 4D hereinafter. Example1 used nickel (Ni) as a material for constituting the selective-growthregion 20. For simplification of drawings, FIGS. 3A to 3D shows oneelectron emitting portion (electron emitting apparatus) or a constituentthereof alone on the cathode electrode (electrically conductive layer)11.

[0216] [Step-100]

[0217] First, an electrically conductive material layer for a cathodeelectrode is formed on the supporting member 10 made, for example, of aglass substrate. Then, the electrically conductive material layer ispatterned by known lithography and a reactive ion etching method (RIEmethod), to form the rectangular cathode electrode (electricallyconductive layer) 11 on the supporting member 10 (see FIG. 3A). At thesame time, a wiring 11A (see FIG. 2) connected to the cathode electrode(electrically conductive layer) 11 is formed on the supporting member10. The electrically conductive material layer is composed, for example,of an approximately 0.2 μm thick aluminum (Al) layer formed by asputtering method.

[0218] [Step-110]

[0219] Then, the selective-growth region 20 is formed on the surface ofthe cathode electrode (electrically conductive layer) 11. Specifically,a resist material layer is first formed on the entire surface by a spincoating method, and then a mask layer 16 composed of the mask materiallayer is formed by lithography so as to expose a surface of a portion ofthe cathode electrode (electrically conductive layer) 11 in whichportion the selective-growth region 20 is to be formed, that is, asurface of the cathode electrode portion (see FIG. 3B). Then, metalparticles are allowed to adhere onto the mask layer 16 and the exposedsurface of the cathode electrode (electrically conductive layer) 11.Specifically, a dispersion prepared by dispersing nickel (Ni) fineparticles in a polysiloxane solution (using isopropyl alcohol as asolvent) is applied to the entire surface by a spin coating method, toform a layer composed of the solvent and the metal particles on thecathode electrode portion. Then, the mask layer 16 is removed, and thesolvent is removed by heating the above layer up to approximately 400°C., to retain the metal particles 21 on the exposed surface of thecathode electrode (electrically conductive layer) 11, whereby theselective-growth region 20 can be obtained (see FIG. 3C). Thepolysiloxane works to fix the metal particles 21 to the exposed surfaceof the cathode electrode (electrically conductive layer) 11 (so-calledadhesive function).

[0220] [Step-120]

[0221] Then, the electron emitting portion 15 comprising thecarbon-group-material layer 23 is formed on the cathode electrode(electrically conductive layer) 11 from a hydrocarbon gas and afluorine-containing hydrocarbon gas. In Example 1, specifically, acarbon-group-material layer 23 having a thickness of approximately 0.2μm is formed on the selective-growth region 20 from a hydrocarbon gasand a fluorine-containing hydrocarbon gas, to obtain the electronemitting portion 15. FIG. 3D shows the thus-formed state. The followingTable 1 shows a forming condition of the carbon-group-material layer 23on the basis of a microwave plasma CVD method. Under the formingcondition of a conventional carbon-group-material layer, a formingtemperature of approximately 900° C. is required. In Example 1, theforming temperature of 500° C. was sufficient for stable formation. Thecarbon-group-material layer does not grow on the cathode electrode(electrically conductive layer) 11 made of aluminum and the wiring 11Amade of aluminum. TABLE 1 [Forming condition of carbon-group-materiallayer] Gas used CH₄/H₂/CF₄ = 100/10/10 SCCM Pressure 1.3 × 10³ PaMicrowave power 500 W (13.56 MHz) Forming temperature 500° C.

[0222] Under the forming condition of the carbon-group-material layershown in Table 1, microscopically, a relatively porous carbon nano-tubeis formed, and at the same time, a fluoride-carbide-containing substance(CF_(x)) is taken into the carbon nano-tube. Macroscopically, thecarbon-group-material layer 23 is formed, and the carbon-group-materiallayer 23 as a whole exhibits a kind of water repellency.

[0223] [Step-130]

[0224] Then, a display is assembled. Specifically, the anode panel APand the cathode panel CP are arranged such that the phosphor layer 31and the electron emitting apparatus (or field emission device) face eachother, and the anode panel AP and the cathode panel CP (morespecifically, the substrate 30 and the supporting member 10) are bondedto each other in their circumferential portions through the frame 34. Inthe bonding, a frit glass is applied to bonding portions of the frame 34and the anode panel AP and bonding portions of the frame 34 and thecathode panel CP. Then, the anode panel AP, the cathode panel CP and theframe 34 are attached. The frit glass is pre-calcined or pre-sintered tobe dried, and then fully calcined or sintered at approximately 450° C.for 10 to 30 minutes. Then, a space surrounded by the anode panel AP,the cathode panel CP, the frame 34 and the frit glass is vacuumedthrough a through-hole (not shown) and a tip tube (not shown), and whenthe space comes to have a pressure of approximately 10⁻⁴ Pa, the tiptube is sealed by thermal fusion. In the above manner, the spacesurrounded by the anode panel AP, the cathode panel CP and the frame 34can be vacuumed. Then, wiring to external circuits is carried out tocomplete the display.

[0225] One example of method of preparing the anode panel AP in thedisplay shown in FIG. 1 will be explained with reference to FIGS. 4A to4D. First, a light-emitting crystal particle composition is prepared.For this purpose, for example, a dispersing agent is dispersed in purewater, and the mixture is stirred with a homo-mixer at 3000 rpm for 1minute. Then, the light-emitting crystal particles are poured into thedispersion of the dispersing agent and pure water, and the mixture isstirred with a homo-mixer at 5000 rpm for 5 minutes. Then, for example,polyvinyl alcohol and ammonium bichromate are added, and the resultantmixture is fully stirred and filtered.

[0226] In the preparation of the anode panel AP, a photosensitivecoating 50 is formed (applied) on the entire surface of a substrate 30made, for example, of glass. Then, the photosensitive coating 50 formedon the substrate 30 is exposed to ultraviolet ray which is radiated froma light source (not shown) and passes through openings 54 formed in amask 53, to form a light-exposed region 51 (see FIG. 4A). Then, thephotosensitive coating 50 is selectively removed by development, toretain a remaining photosensitive coating portion (exposed and developedphotosensitive coating) 52 on the substrate 30 (see FIG. 4B). Then, acarbon agent (carbon slurry) is applied to the entire surface, dried andcalcined or sintered, and then, the remaining photosensitive coatingportion 52 and the carbon agent thereon are removed by a lift-offmethod, whereby a black matrix 32 composed of the carbon agent is formedon the exposed substrate 30, and at the same time, the remainingphotosensitive coating portion 52 is removed (see FIG. 4C). Then,phosphor layers 31 of red, green and blue are formed on the exposedsubstrate 30 (see FIG. 4D). Specifically, the light-emitting crystalparticle compositions prepared from the light-emitting crystal particles(phosphor particles) are used. For example, a red photosensitivelight-emitting crystal particle composition (phosphor slurry) is appliedto the entire surface, followed by exposure to ultraviolet ray anddevelopment. Then, a green photosensitive light-emitting crystalparticle composition (phosphor slurry) is applied to the entire surface,followed by exposure to ultraviolet ray and development. Further, a bluephotosensitive light-emitting crystal particle composition (phosphorslurry) is applied to the entire surface, followed by exposure toultraviolet ray and development. Then, the anode electrode 33 composedof an approximately 0.07 μm thick aluminum thin film is formed on thephosphor layers 31 and the black matrix 32 by a sputtering method.Alternatively, each phosphor layer 31 can be also formed by ascreen-printing method or the like.

[0227] In the display having the above constitution, the electronemitting portion of each electron emitting apparatus comprises the flatcarbon-group-material layer 23 having a low work function, and thefabrication thereof does not require such complicated and advancedfabrication techniques as have been required concerning the conventionalSpindt type field emission device. Moreover, the etching of thecarbon-group-material layer 23 is no longer required. When the area ofthe effective field of a display increases and when the number ofelectron emitting portions to be formed increases accordingly to a greatextent, the electron emission efficiency of the electron emittingportions can be rendered uniform throughout the entire region of theeffective field, and there can be realized a display which is remarkablyfree of non-uniformity in brightness and has high image quality.

[0228] The pressure inside the display was adjusted to 1×10⁻⁵ Pa(mainly, nitrogen gas was present), the H₂O partial pressure was set at1×10⁻⁶ Pa, and the display was measured for electron emissionproperties. In addition, a display was manufactured by forming acarbon-group-material layer without using CF₄ under the formingcondition of the carbon-group-material layer shown in Table 1, and thedisplay was used as Comparative Example. As a result, the deteriorationof properties of the electron emitting portion of the display of Example1 was remarkably small as compared with the counterpart of the displayof Comparative Example.

EXAMPLE 2

[0229] Example 2 is concerned with the electron emitting apparatusaccording to the second aspect (more specifically, second-A aspect) ofthe present invention and the manufacturing method thereof, the fieldemission device according to the second aspect (more specifically,second-A aspect), the manufacturing method of a field emission deviceaccording to the second aspect (more specifically, second-A andsecond-A(1) aspects), the display according to the second aspect (morespecifically, second-A aspect), and the manufacturing method of adisplay according to the second aspect (more specifically, second-A andsecond-A(1) aspects).

[0230] Since the display of Example 2 can have the same structure asthat of the display of Example 1, the detailed explanation thereof isomitted. FIG. 5 shows a schematic partial cross-sectional view of oneelectron emitting apparatus or field emission device. The schematicpartial cross-sectional view of the display of Example 2 and theschematic perspective view of one field emission device or one electronemitting portion are as shown in FIGS. 1 and 2.

[0231] The electron emitting apparatus or field emission device inExample 2 also comprises a cathode electrode (electrically conductivelayer) 11 having a selective-growth region 20 formed on its surface, andan electron emitting portion 15 formed on the selective-growth region20. The selective-growth region 20 is constituted of metal particles 21adhering to the surface of the cathode electrode (electricallyconductive layer) 11. Further, the electron emitting portion comprises acarbon-group-material layer 23 and a fluoride-carbide-containing thinfilm (CF_(x) thin film) 24 formed on the surface of thecarbon-group-material layer. The carbon-group-material layer 23 isformed from a hydrocarbon gas (specifically, CH₄), and thefluoride-carbide-containing thin film 24 is formed from afluorine-containing hydrocarbon gas (specifically, CH₂F₂).

[0232] The manufacturing method of the electron emitting apparatus, thefield emission device and the display in Example 2 will be explainedbelow. Example 2 used zinc (Zn) as a material for constituting theselective-growth region 20.

[0233] [Step-200]

[0234] A cathode electrode (electrically conductive layer) 11 made ofaluminum (Al) and a wiring 11A made of aluminum (Al) are formed on asupporting member 10 made, for example, of a glass substrate in the samemanner as in [Step-100] of Example 1

[0235] [Step-210]

[0236] Then, a selective-growth region 20 is formed on the surface ofthe cathode electrode (electrically conductive layer) 11 in the samemanner as in [Step-110] of Example 1. However, Example 2 used a solutionof fine zinc (Zn) particles dispersed in a polysiloxane solution (usingisopropyl alcohol as a solvent).

[0237] [Step-220]

[0238] Then, the carbon-group-material layer is formed on the cathodeelectrode (electrically conductive layer) 11 from a hydrocarbon gas. InExample 2, specifically, a carbon-group-material layer 23 having athickness of approximately 0.2 μm is formed on the selective-growthregion 20 from a hydrocarbon gas. Table 2 shows a forming condition ofthe carbon-group-material layer 23 based on a microwave plasma CVDmethod. Under the forming condition of a conventionalcarbon-group-material layer, a forming temperature of approximately 900°C. is required. In Example 2, the forming temperature of 500° C. wassufficient for stable formation. The carbon-group-material layer doesnot grow on the cathode electrode (electrically conductive layer) 11made of aluminum and the wiring 11A made of aluminum. TABLE 2 [Formingcondition of carbon-group-material layer] Gas used CH₄/H₂ = 100/10 SCCMPressure 1.3 × 10³ Pa Microwave power 500 W (13.56 MHz) Formingtemperature 400° C.

[0239] [Step-230]

[0240] Then, a fluoride-carbide-containing thin film (CF_(x) thin film)24 is formed on the surface of the carbon-group-material layer 23 from afluorine-containing hydrocarbon gas, thereby to obtain an electronemitting portion 15 comprising the carbon-group-material layer 23 andthe fluoride-carbide-containing thin film 24 formed on the surface ofthe carbon-group-material layer 23. The following Table 3 shows aforming condition of the fluoride-carbide-containing thin film (CF_(x)thin film) 24 based on a microwave plasma CVD method. TABLE 3 [Formingcondition of fluoride-carbide-containing thin film] Gas used CH₂F₂ = 100SCCM Pressure 1.3 × 10³ Pa Microwave power 500 W (13.56 MHz) Formingtemperature 400° C.

[0241] Under the forming condition of the fluoride-carbide-containingthin film (CF_(x) thin film) 24 shown in Table 3, thefluoride-carbide-containing thin film (CF_(x) thin film) 24 is formed onthe surface of the carbon nano-tube, and the electron emitting portion15 as a whole exhibits a kind of water repellency.

[0242] [Step-240]

[0243] Then, a display is assembled in the same manner as in [Step-130]of Example 1.

[0244] The pressure inside the display was adjusted to 1×10⁻⁵ Pa(mainly, nitrogen gas was present), the H₂O partial pressure was set at1×10⁻⁶ Pa, and the display was measured for electron emissionproperties. In addition, a display was similarly manufactured without[Step-230] and used as Comparative Example. As a result, thedeterioration of properties of the electron emitting portion of thedisplay of Example 2 was remarkably small as compared with thecounterpart of the display of Comparative Example.

EXAMPLE 3

[0245] Example 3 is concerned with the electron emitting apparatusaccording to the third aspect (more specifically, third-A aspect) of thepresent invention and the manufacturing method thereof, the fieldemission device according to the third aspect (more specifically,third-A aspect), the manufacturing method of a field emission deviceaccording to the third aspect (more specifically, the third-A andthird-A(1) aspects), the display according to the third aspect (morespecifically, third-A aspect), and the manufacturing method of a displayaccording to the third aspect (more specifically, the third-A aspect andthird-A(1) aspect).

[0246] The electron emitting apparatus, the field emission device andthe display in Example 3 can have the same constitutions as those inExample 1, so that the detailed explanations thereof are omitted. Theschematic partial cross-sectional view of the display and the schematicperspective view and the schematic partial cross-sectional view of onefield emission device or one electron emitting apparatus in Example 3are as shown in FIG. 1, FIG. 2 and FIG. 3D.

[0247] The electron emitting apparatus or field emission device inExample 3 also comprises a cathode electrode (electrically conductivelayer) 11 having a selective-growth region 20 formed on its surface, andan electron emitting portion 15 formed on the selective-growth region20. The selective-growth region 20 is constituted of metal particles 21adhering to the surface of the cathode electrode (electricallyconductive layer) 11. The electron emitting portion comprises acarbon-group-material layer 23. The carbon-group-material layer 23 is alayer formed from a hydrocarbon gas (specifically, CH₄). The surface ofthe carbon-group-material layer 23 is terminated (modified) withfluorine atoms. That is, C—H bonds present in the surface of thecarbon-group-material layer 23 are replaced with C—F bonds, and thecarbon-group-material layer 23 as a whole therefore exhibits a kind ofwater repellency.

[0248] The manufacturing method of the electron emitting apparatus, thefield emission device and the display in Example 3 will be explainedbelow. Example 3 used aluminum (Al) for the cathode electrode(electrically conductive layer) 11 and used a cobalt-nickel alloy as amaterial for constituting the selective-growth region 20.

[0249] [Step-300]

[0250] First, the cathode electrode (electrically conductive layer) 11made of aluminum (Al) and a wiring 11A made of aluminum (Al) are formedon a supporting member 10 made, for example, of a glass substrate in thesame manner as in [Step-100] in Example 1.

[0251] [Step-310]

[0252] Then, the selective-growth region 20 is formed on the surface ofthe cathode electrode (electrically conductive layer) 11 in the samemanner as in [Step-110] in Example 1. However, Example 3 used a solutionof cobalt-nickel alloy (Co—Ni alloy) fine particles dispersed in apolysiloxane solution (using isopropyl alcohol as a solvent).

[0253] [Step-320]

[0254] Then, a carbon-group-material layer is formed on the cathodeelectrode (electrically conductive layer) 11 from a hydrocarbon gas. InExample 3, specifically, a carbon-group-material layer 23 having athickness of approximately 0.2 μm is formed on the selective-growthregion 20 from a hydrocarbon gas. The following Table 4 shows a formingcondition of the carbon-group-material layer 23 based on an ICP-CVDmethod. Under the forming condition of a conventionalcarbon-group-material layer, a forming temperature of approximately 900°C. is required. In Example 3, the forming temperature of 400° C. wassufficient for stable formation. The carbon-group-material layer doesnot grow on the cathode electrode (electrically conductive layer) 11made of aluminum and the wiring 11A made of aluminum. TABLE 4 [Formingcondition of carbon-group-material layer] Gas used CH₄/H₂ = 100/10 SCCMPressure 1.3 × 10³ Pa Microwave power 500 W (13.56 MHz) Formingtemperature 400° C.

[0255] [Step-330]

[0256] Then, the surface of the carbon-group-material layer 23 isterminated (modified) with a fluorine-containing hydrocarbon gas,thereby to obtain an electron emitting portion 15 comprising thecarbon-group-material layer 23 whose surface is terminated (modified)with fluorine atoms. The following Table 5 shows a termination(modification) condition of the carbon-group-material layer 23 based onan ICP-CVD method. TABLE 5 [Termination condition of surface ofcarbon-group-material layer] Gas used CF₄ = 100 SCCM Pressure 1.3 × 10³Pa ICP power 500 W (13.56 MHz) Forming temperature 400° C.

[0257] Under the termination (modification) condition of thecarbon-group-material layer shown in Table 5, CF₄ gas is used unlike theforming condition of the fluoride-carbide-containing thin film (CF, thinfilm) 24 shown in Table 3, so that the content of the fluorine componentconstituting the fluorine-containing hydrocarbon gas is high and thatthe deposition of the fluoride-carbide-containing thin film (CF_(x) thinfilm) based on the fluorine-containing hydrocarbon gas is hencedifficult. The surface of the carbon nano-tube is terminated (modified)with fluorine atoms, that is, C—H bonds are replaced with C—F bonds, sothat the carbon-group-material layer 23 as a whole exhibits a kind ofwater repellency.

[0258] [Step-340]

[0259] Then, a display is assembled in the same manner as in [Step-130]in Example 1.

[0260] The pressure inside the display was adjusted to 1×10⁻⁵ Pa(mainly, nitrogen gas was present), the H₂O partial pressure was set at1×10⁻⁶ Pa, and the display was measured for electron emissionproperties. In addition, a display was similarly manufactured without[Step-330] and used as Comparative Example. As a result, thedeterioration of properties of the electron emitting portion of thedisplay of Example 3 was remarkably small as compared with thecounterpart of the display of Comparative Example.

Example 4

[0261] Example 4 are concerned with variants of the electron emittingapparatus, the field emission device and the display and themanufacturing methods of them, explained in Example 1. In themanufacturing method explained in Example 1, the metal particles 21 wereallowed to adhere onto the cathode electrode portion. In Example 4, thestep of forming a selective-growth region comprises the step of forminga metal thin film made of titanium (Ti) on the basis of a sputteringmethod. The manufacturing method of the electron emitting apparatus, thefield emission device and the display in Example 4 will be explainedbelow with reference to FIGS. 6A and 6B. For simplification of drawings,FIGS. 6A and 6B show one electron emitting portion (electron emittingapparatus) on a cathode electrode (electrically conductive layer) 11 ortheir constituting elements alone.

[0262] [Step-400]

[0263] First, a cathode electrode (electrically conductive layer) 11 isformed on a supporting member 10 made, for example, of a glass substratein the same manner as in [Step-100] in Example 1. Then, a resistmaterial layer is formed on the entire surface by a spin coating method,and a lithographical method is applied to form a mask layer (made of theresist material layer) where the surface of the cathode electrodeportion is exposed.

[0264] [Step-410]

[0265] Then, a metal thin film 22 is formed on the mask layer includingthe exposed surface of the cathode electrode (electrically conductivelayer) 11 by a sputtering method under a condition shown in Table 6.Then, the mask layer is removed (see FIG. 6A). In this manner, aselective-growth region 20 comprising the metal thin film 22 formed onthe cathode electrode portion can be obtained. TABLE 6 [Formingcondition of metal thin film] Target Ti Process gas Ar = 100 SCCM DCpower 4 kW Pressure 0.4 Pa Supporting member heating 150° C. temperatureFilm thickness 30 nm

[0266] [Step-420]

[0267] Then, a carbon-group-material layer 23 having a thickness ofapproximately 0.2 μm is formed on the selective-growth region 20 in thesame manner as in [Step-120] in Example 1, to obtain an electronemitting portion (see FIG. 6B). Then, a display is assembled in the samemanner as in [Step-130] in Example 1.

[0268] When [Step-220] and [Step-230] in Example 2 are carried out in[Step-420], the electron emitting apparatus or the display according tothe second aspect of the present invention can be obtained.

[0269] Alternatively, when [Step-320] and [Step-330] in Example 3 arecarried out, the electron emitting apparatus or the display according tothe third aspect of the present invention can be obtained.

EXAMPLE 5

[0270] Example 5 is concerned with the electron emitting apparatusaccording to the first aspect of the present invention, the fieldemission device and the manufacturing method thereof according to thefourth aspect of the present invention, and the display and themanufacturing method thereof according to the fourth aspect of thepresent invention. Displays in Examples 5 to 20 are so-called“three-electrodes” type displays.

[0271]FIG. 7 shows a schematic partial end view of the display ofExample 5, and FIG. 8B shows a basic constitution of the field emissiondevice or electron emitting apparatus. The schematic partial perspectiveview obtained when a cathode panel CP and an anode panel AP areseparated is substantially as shown in FIG. 21.

[0272] The field emission device or the electron emitting apparatus ofExample 5 has a cathode electrode (corresponding to an electricallyconductive layer) 11 formed on a supporting member 10 and a gateelectrode 13 which is formed above the cathode electrode 11 and has anopening portion (first opening portion 14A). The field emission deviceor the electron emitting apparatus further has an electron emittingportion 15 comprising a carbon-group-material layer 23 formed on asurface of a portion of a cathode electrode 11 which portion ispositioned in a bottom portion of the first opening portion 14A. Aninsulating layer 12 is formed on the supporting member 10 and thecathode electrode 11, and a second opening portion 14B communicatingwith the first opening portion 14A formed in the gate electrode 13 isformed in the insulating layer 12. In Example 5, the cathode electrode(electrically conductive layer) 11 is composed of copper (Cu).

[0273] The display of Example 5 is also constituted of a cathode panelCP having a number of electron emitting regions, provided with theabove-mentioned field emission devices and formed in an effective fieldin the form of a two-dimensional matrix and an anode panel AP, and thedisplay has a plurality of pixels. The cathode panel CP and the anodepanel AP are bonded to each other in their circumferential portionsthrough a frame 34. Further, a through-hole 36 for vacuuming is formedin an ineffective field of the cathode panel CP, and a tip tube 37 whichis to be sealed after vacuuming is connected to the through-hole 36. Theframe 34 is made of ceramic and has a height, for example, of 1.0 mm. Insome cases, an adhesive layer alone may be used in place of the frame34.

[0274] The anode panel AP can have the same structure as that explainedin Example 1, so that a detailed explanation thereof is omitted.

[0275] Each pixel is constituted of the cathode electrode 11 having theform of a stripe, the electron emitting portion 15 formed thereon and aphosphor layer 31 arranged in the effective field of the anode panel APso as to face the field emission device. In the effective field, suchpixels are arranged on the order of hundreds of thousands to severalmillions.

[0276] A relatively negative voltage is applied to the cathode electrode11 from a cathode-electrode control circuit 40, a relatively positivevoltage is applied to the gate electrode 13 from a gate-electrodecontrol circuit 41, and a higher positive voltage than the voltage tothe gate electrode 13 is applied to the anode electrode 33 from ananode-electrode control circuit 42. When such a display is used fordisplaying, for example, a scanning signal is inputted to the cathodeelectrode 11 from the cathode-electrode control circuit 40, and a videosignal is inputted to the gate electrode 13 from the gate-electrodecontrol circuit 41. Alternatively, it may be employed the constitutionin which the video signal is inputted to the cathode electrode 11 fromthe cathode-electrode control circuit 40, and the scanning signal isinputted to the gate electrode 13 from the gate-electrode controlcircuit 41. Electrons are emitted from the electron emitting portion 15on the basis of a quantum tunnel effect due to an electric filedgenerated when a voltage is applied between the cathode electrode 11 andthe gate electrode 13, and the electrons are attracted toward the anodeelectrode 33 and collide with the phosphor layer 31. As a result, thephosphor layer 31 is excited to emit light, and a desired image can beobtained.

[0277] The manufacturing method of the electron emitting apparatus, thefield emission device and the display in Example 5 will be explainedbelow with reference to FIGS. 8A and 8B. For simplification of drawings,FIGS. 8A and 8B show one electron emitting portion in an overlappingregion of a cathode electrode 11 and a gate electrode 13 or theirconstituting elements alone.

[0278] [Step-500]

[0279] First, an electrically conductive material layer for a cathodeelectrode is formed on the supporting member 10 made, for example, of aglass substrate. Then, the electrically conductive material layer ispatterned by known lithography and a known RIE method, to form thecathode electrode (electrically conductive layer) 11 having the form ofa stripe on the supporting member 10. The cathode electrode(electrically conductive layer) 11 in the form of a stripe extendsleftward and rightward on the paper surface of the drawing. Theelectrically conductive material layer is composed, for example, of anapproximately 0.2 μm thick copper (Cu) layer formed by a sputteringmethod.

[0280] [Step-510]

[0281] Then, the insulating layer 12 is formed on the supporting member10 and the cathode electrode 11. Specifically, the insulating layer 12having a thickness of approximately 1 μm is formed on the entiresurface, for example, by a CVD method using TEOS (tetraethoxysilane) asa source gas. Table 7 shows one example of a condition of forming theinsulating layer 12. TABLE 7 (Condition of forming insulating layer)TEOS flow rate 800 SCCM O₂ flow rate 600 SCCM Pressure 1.1 kPa RF power0.7 kW (13.56 MHz) Film forming temperature 400° C.

[0282] [step-520]

[0283] Then, the gate electrode 13 having the first opening portion 14Ais formed on the insulating layer 12. Specifically, an electricallyconductive material layer composed of aluminum (Al) for a gate electrodeis formed on the insulating layer 12 by a sputtering method, and then afirst mask material layer (not shown) patterned is formed on theelectrically conductive material layer. The electrically conductivematerial layer is etched with using the first mask material layer as anetching mask to pattern the electrically conductive material layer inthe form of a stripe, and then the first mask material layer is removed.Then, a second mask material layer (not shown) patterned is formed onthe electrically conductive material layer and the insulating layer 12,and the electrically conductive material layer is etched with using thesecond mask material layer as an etching mask. In this manner, the gateelectrode 13 having the first opening portion 14A can be formed on theinsulating layer 12. The gate electrode 13 in the form of a stripeextends in a direction (for example, direction perpendicular to thepaper surface of the drawing) different from the direction of thecathode electrode 11. Thereafter, the second opening portion 14Bcommunicating with the first opening portion 14A formed in the gateelectrode 13 is formed in the insulating layer 12. Specifically, theinsulating layer 12 is etched by an RIE method using the second maskmaterial layer as an etching mask, and then the second mask materiallayer is removed. In this manner, a structure shown in FIG. 8A can beobtained. Table 8 shows a condition of etching the insulating layer 12.In Example 5, the first opening portion 14A and the second openingportion 14B has a one-to-one correspondence relationship. That is, onesecond opening portion 14B is formed per first opening portion 14A. Whenviewed as a plan view, the first and the second opening portions 14A and14B have the form of a circle having a diameter of 1 to 30 μm. It issufficient to form the opening portions 14A and 14B in the quantity ofapproximately 1 to 3000 per pixel. TABLE 8 (Condition of etchinginsulating layer) Parallel plate reactive Etching apparatus ion etchingsystem C₄F₈ flow rate  30 SCCM CO flow rate  70 SCCM Ar flow rate 300SCCM Pressure 7.3 Pa RF power 1.3 kW (13.56 MHz) Etching temperatureroom temperature

[0284] [Step-530]

[0285] Then, the electron emitting portion 15 comprising thecarbon-group-material layer 23 is formed on the surface of a portion ofthe cathode electrode 11 which portion is positioned in a bottom portionof the opening portions 14A and 14B. The cathode electrode 11 iscomposed of a copper (Cu) which works as a kind of a catalyst.Specifically, the carbon-group-material layer 23 having a thickness ofapproximately 0.2 μm is formed on the portion of the cathode electrode11 to obtain the electron emitting portion 15 in the same manner as in[Step-120] in Example 1. FIG. 8B shows the thus-obtained state. Acondition of forming the carbon-group-material layer 23 according to amicrowave plasma CVD method may be the same condition as that shown inTable 1. Since the gate electrode 13 is formed of aluminum (Al), nocarbon-group-material layer is formed on the gate electrode 13.

[0286] [Step-540]

[0287] A display is assembled in the same manner as in [Step-130] inExample 1.

[0288] In Example 5, the electron emitting portion 15 comprising thecarbon-group-material layer 23 is formed on the portion of the cathodeelectrode 11 which portion is positioned in the bottom portion of theopening portions 14A and 14B and the cathode electrode 11 is composed ofa material which works as a kind of a catalyst, so that it is no longernecessary to pattern the carbon-group-material layer 23 to bring it intoa desired form.

[0289] Even when the copper (Cu) is replaced with silver (Ag) or gold(Au) to constitute the cathode electrode or the electrically conductivelayer, these metals work as a kind of catalyst, and the electronemitting portion 15 comprising the carbon-group-material layer 23 can beformed on the cathode electrode 11.

EXAMPLE 6

[0290] Example 6 is a variant of Example 5. In the manufacturing methodof an electron emitting apparatus, the manufacturing method of a fieldemission device and the manufacturing method of a display explained inExample 5, the surface of the cathode electrode 11 is naturallyoxidized, so that it is sometimes difficult to form thecarbon-group-material layer 23. In Example 6, the metal oxide (so-callednatural oxide film) is removed from the surface of the cathode electrodeportion. The metal oxide on the surface of the cathode electrode portioncan be removed by plasma reduction treatment or washing.

[0291] The electron emitting apparatus, the field emission device andthe display to be produced in Example 6 or Example 7 to be describedlater are structurally the same as those in Example 5, so that detailedexplanations thereof are omitted. The manufacturing method of anelectron emitting apparatus, the manufacturing method of a fieldemission device and the manufacturing method of a display in Example 6will be explained below.

[0292] [Step-600]

[0293] First, in the same manner as in [Step-500] to [Step-520] inExample 5, a cathode electrode 11 is formed on a supporting member 10made, for example, of a glass substrate; then, an insulating layer 12 isformed on the supporting member 10 and the cathode electrode 11; then, agate electrode 13 having a first opening portion 14A is formed on theinsulating layer 12; and then, a second opening portion 14Bcommunicating with the first opening portion 14A formed in the gateelectrode 13 is formed in the insulating layer 12.

[0294] [Step-610]

[0295] Then, the metal oxide (natural oxide film) on the surface of theportion of the cathode electrode 11 which portion is exposed in thebottom portion of the opening portions 14A and 14B is removed by plasmareduction treatment (microwave plasma treatment) under a condition shownin Table 9. Otherwise, the metal oxide (natural oxide film) on theexposed surface of the cathode electrode portion can be removed, forexample, with a 50% hydrofluoric acid aqueous solution/pure watermixture having a 50% hydrofluoric acid aqueous solution:pure watermixing ratio of 1:49 (volume ratio). TABLE 9 Gas used H₂ = 100 SCCMPressure 1.3 × 10³ Pa Microwave power 600 W (13.56 MHz) Treatingtemperature 400° C.

[0296] [Step-620]

[0297] Then, the carbon-group-material layer 23 having a thickness ofapproximately 0.2 μm is formed on the portion of the cathode electrode11 which portion is exposed in the bottom portion of the openingportions 14A and 14B, to obtain the electron emitting portion 15 in thesame manner as in [Step-120] in Example 1. A condition of forming thecarbon-group-material layer 23 according to a microwave plasma CVDmethod may be the same condition as that shown in Table 1.

[0298] [Step-630]

[0299] Then, the display is assembled in the same manner as in[Step-130] in Example 1.

[0300] In Example 6, the metal oxide (natural oxide film) on the portionof the cathode electrode 11 which portion is exposed in the bottomportion of the opening portions 14A and 14B is removed, and then thecarbon-group-material layer is formed on the cathode electrode portion,so that the carbon-group-material layer having more excellent propertiescan be formed.

EXAMPLE 7

[0301] Example 7 is also a variant of Example 5. In Example 7, aconvexo-concave shape is formed in the portion of the cathode electrode11 which portion is exposed in the bottom portion of the openingportions 14A and 14B. Protrusions are therefore formed in thecarbon-group-material layer formed thereon. As a result, a fieldemission device having high electron emission efficiency can beobtained. The manufacturing method of a field emission device and themanufacturing method of a display in Example 7 will be explained below.

[0302] [Step-700]

[0303] First, in the same manner as in [Step-500] to [Step-520] inExample 5, a cathode electrode 11 is formed on a supporting member 10made, for example, of a glass substrate; then, an insulating layer 12 isformed on the supporting member 10 and the cathode electrode 11; then, agate electrode 13 having a first opening portion 14A is formed on theinsulating layer 12; and then, a second opening portion 14Bcommunicating with the first opening portion 14A formed in the gateelectrode 13 is formed in the insulating layer 12.

[0304] [Step-710]

[0305] Then, the surface of the portion of the cathode electrode 11which portion is positioned in the bottom portion of the openingportions 14A and 14B is etched to form a convexo-concave shape. Table 10shows a condition of the above etching. TABLE 10 Etching solution 1%hydrochloric acid aqueous solution Treatment time 5 minutes period

[0306] [Step-720]

[0307] Then, a step similar to [Step-530] in Example 5 is carried out toform an electron emitting portion 15 comprising a carbon-group-materiallayer 23 on the portion of the cathode electrode 11 which portion ispositioned in the bottom portion of the opening portions 14A and 14B.Specifically, the carbon-group-material layer 23 having a thickness ofapproximately 0.2 μm is formed on the portion of the cathode electrode11 to obtain the electron emitting portion 15 in the same manner as in[Step-120] in Example 1. A condition of forming thecarbon-group-material layer 23 according to a microwave plasma CVDmethod may be the same condition as that shown in Table 1.

[0308] [Step-730]

[0309] Then, the display is assembled in the same manner as in[Step-130] in Example 1.

[0310] The step of forming the convexo-concave shape on the portion ofthe cathode electrode 11 which portion is exposed in the bottom portionof the opening portions 14A and 14B, explained in Example 7, can beapplied to Example 6. Further, the removal of the metal oxide (naturaloxide film) explained in Example 6 can be applied to Example 7.

[0311] When [Step-220] and [Step-230] are carried out in the step offorming the carbon-group-material layer or the electron emitting portionin Examples 5 to 7 explained above, the electron emitting apparatusaccording to the second aspect of the present invention, the fieldemission device according to the fifth-A aspect of the present inventionand the display according to the fifth-A aspect of the present inventioncan be obtained, and it comes to mean that the manufacturing method of afield emission device according to the fifth-A aspect of the presentinvention and the manufacturing method of a display according to thefifth-A aspect of the present invention are carried out.

[0312] Further, when [Step-320] and [Step-330] in Example 3 are carriedout in the step of forming the carbon-group-material layer or theelectron emitting portion in Examples 5 to 7 explained above, theelectron emitting apparatus according to the third aspect of the presentinvention, the field emission device according to the sixth-A aspect ofthe present invention and the display according to the sixth-A aspect ofthe present invention can be obtained, and it comes to mean that themanufacturing method of a field emission device according to the sixth-Aaspect of the present invention and the manufacturing method of adisplay according to the sixth-A aspect of the present invention arecarried out.

EXAMPLE 8

[0313] Example 8 is concerned with the electron emitting apparatushaving a selective-growth region according to the first aspect of thepresent invention, the field emission device having a selective-growthregion according to the fourth aspect of the present invention, thedisplay having a selective-growth region according to the fourth aspectof the present invention, the manufacturing method of a field emissiondevice according to the fourth (2) aspect of the present inventionincluding the step of forming a selective-growth region, and themanufacturing method of a display according to the fourth (2) aspect ofthe present invention including the step of forming a selective-growthregion.

[0314]FIG. 12B shows a schematic partial end view of the field emissiondevice or the electron emitting apparatus of Example 8. FIG. 9 shows aschematic partial end view of the display of Example 8. The fieldemission device or the electron emitting apparatus has a cathodeelectrode (corresponding to the electrically conductive layer) 11 formedon a supporting member 10 and a gate electrode 13 which is formed abovethe cathode electrode 11 and has a first opening portion 14A. The fieldemission device or the electron emitting apparatus further has aselective-growth region 20 formed on a surface of a portion of thecathode electrode 11 which portion is positioned in a bottom portion ofthe opening portions 14A and 14B, and an electron emitting portioncomprising a carbon-group-material layer 23 formed on theselective-growth region 20. In Example 8, the selective-growth region 20is constituted of metal particles 21 composed of nickel (Ni) adhere onthe surface of the cathode electrode.

[0315] In the field emission device of Example 8, an insulating layer 12is formed on the supporting member 10 and the cathode electrode 11, thesecond opening portion 14B communicating with the first opening portion14A formed in the gate electrode 13 is formed in the insulating layer12, and the selective-growth region and the carbon-group-material layer23 is positioned in the bottom portion of the second opening portion14B.

[0316]FIG. 9 shows a constitution example of the display of Example 8.The display comprises a cathode panel CP having a large number of theelectron emitting regions formed in an effective region in the form of atwo-dimensional matrix, and an anode panel AP, and the display has aplurality of pixels. Each pixel is constituted of the field emissiondevice, an anode electrode 33 and a phosphor layer 31 formed on asubstrate 30 so as to be opposed to the field emission device. Thecathode panel CP and the anode panel AP are bonded in theircircumferential portions through a frame 34. In the partial end view ofFIG. 9, two opening portions (14A and 14B) and two carbon-group-materiallayers 23 which are electron emitting portions are shown per cathodeelectrode 11 on the cathode panel CP, for simplifying the drawing.However, the number of each of these members shall not be limitedthereto. The basic constitution of the field emission device is as shownin FIG. 12B. Further, a through-hole 36 for vacuuming is provided in anineffective field of the cathode panel CP, and a tip tube 37 which issealed after vacuuming is connected to the through-hole 36. FIG. 9 showsa completed state of the display, and the shown tip tube 37 is alreadysealed.

[0317] The anode panel AP can have the same structure as that explainedin Example 1, so that a detailed explanation thereof is omitted.

[0318] The operation of the display for displaying can be the same asthe operation of the display explained in Example 5, so that a detailedexplanation thereof is omitted.

[0319] The manufacturing method of an electron emitting apparatus, themanufacturing method of a field emission device and the manufacturingmethod of a display in Example 8 will be explained below with referenceto FIGS. 10A to 10C, FIGS. 11A and 11B and FIGS. 12A and 12B. Forsimplification of drawings, these Figures show one electron emittingportion in an overlapping region of a cathode electrode 11 and a gateelectrode 13 or their constituting elements alone.

[0320] [Step-800]

[0321] First, an electrically conductive material layer for a cathodeelectrode is formed on the supporting member 10 made, for example, of aglass substrate, and the electrically conductive material layer is thenpatterned by known lithography and a known RIE method, to form thecathode electrode (corresponding to the electrically conductive layer)11 in the form of a stripe on the supporting member 10 (see FIG. 10A).The cathode electrode 11 in the form of a stripe extends leftward andrightward on the paper surface of the drawing. The electricallyconductive material layer is composed, for example, of an approximately0.2 μm thick aluminum (Al) layer formed by a sputtering method.

[0322] [Step-810]

[0323] Then, an insulating layer 12 is formed on the supporting member10 and the cathode electrode 11. Specifically, the insulating layer 12having a thickness of approximately 1 μm is formed on the entiresurface, for example, by a CVD method using TEOS (tetraethoxysilane) asa source gas. The insulating layer 12 can be formed under the samecondition as that shown in Table 7.

[0324] [Step-820]

[0325] Then, the gate electrode 13 having the first opening portion 14Ais formed on the insulating layer 12. Specifically, an electricallyconductive material layer composed of aluminum (Al) for a gate electrodeis formed on the insulating layer 12 by a sputtering method, and then apatterned first mask material layer (not shown) is formed on theelectrically conductive material layer. The electrically conductivematerial layer is then etched with using the above first mask materiallayer as an etching mask and patterned in the form of a stripe, and thenthe first mask material layer is removed. Then, a patterned second maskmaterial layer (not shown) is formed on the electrically conductivematerial layer and the insulating layer 12, and the electricallyconductive material layer is etched with using the above second maskmaterial layer as an etching mask. In this manner, the gate electrode 13having the first opening portion 14A can be formed on the insulatinglayer 12. The gate electrode 13 in the form of a stripe extends in adirection (direction perpendicular to the paper surface of the drawing)different from the direction in which the cathode electrode 11 extends.

[0326] [Step-830]

[0327] Then, the second opening portion 14B communicating with the firstopening portion 14A formed in the gate electrode 13 is formed-in theinsulating layer 12. Specifically, the insulating layer 12 is etched byan RIE method with using the second mask material layer as an etchingmask, and then the second mask material layer is removed. In thismanner, a structure shown in FIG. 10B can be obtained. The insulatinglayer 12 can be etched under the same condition as that shown in Table8. In Example 8, the first opening portion 14A and the second openingportion 14B have a one-to-one correspondence relationship. That is, onesecond opening portion 14B is formed per first opening portion 14A. Whenviewed as a plan view, the first and second opening portions 14A and 14Bhave the form, for example, of a circle having a diameter of 1 to 30 μm.It is sufficient to form 1 to approximately 3000 opening portions 14Aand 14B per pixel.

[0328] [Step-840]

[0329] Then, the selective-growth region 20 is formed on the portion ofthe cathode electrode 11 which portion is positioned in the bottomportion of the second opening portion 14B. For this purpose, first, amask layer 116 is formed so as to expose the surface of the cathodeelectrode 11 in a central portion of the bottom portion of the secondopening portion 14B (see FIG. 10C). Specifically, a resist materiallayer is formed on the entire surface including the inner surfaces ofthe opening portions 14A and 14B by a spin coating method, and then ahole is formed in the resist material layer positioned in the centralportion of the bottom portion of the second opening portion 14B bylithography, whereby the mask layer 116 can be obtained. In Example 8,the mask layer 116 covers part of the cathode electrode 11 which part ispositioned in the bottom portion of the second opening portion 14B, aside wall of the second opening portion 14B, a side wall of the firstopening portion 14A, the gate electrode 13 and the insulating layer 12.While the selective-growth region is to be formed on the portion of thecathode electrode 11 which portion is positioned in the central portionof the bottom portion of the second opening portion 14B in a step tocome thereafter, the above mask layer can reliably preventshort-circuiting between the cathode electrode 11 and the gate electrode13 with metal particles.

[0330] Then, metal particles are allowed to adhere onto the mask layer116 and the exposed surface of the cathode electrode 11. Specifically, adispersion prepared by dispersing nickel (Ni) fine particles in apolysiloxane solution (using isopropyl alcohol as a solvent) is appliedto the entire surface by a spin coating method, to form a layer composedof the solvent and the metal particles on the cathode electrode portion.Then, the mask layer 116 is removed, and the solvent is removed byheating the above layer up to approximately 400° C., to retain the metalparticles 21 on the exposed surface of the cathode electrode 11, wherebythe selective-growth region 20 can be obtained (see FIG. 11A). Thepolysiloxane works to fix the metal particles 21 to the exposed surfaceof the cathode electrode 11 (so-called adhesive function).

[0331] [Step-850]

[0332] Then, the carbon-group-material layer 23 having a thickness ofapproximately 0.2 μm is formed on the selective-growth region 20, toobtain an electron emitting portion in the same manner as in [Step-120]in Example 1. FIGS. 11B and 12A show the thus-obtained state. FIG. 11Bis a schematic partial end view obtained when the field emission deviceis viewed from a direction in which the gate electrode 13 extends. FIG.12A is a schematic partial end view obtained when the field emissiondevice is viewed from a direction in which the cathode electrode 11extends. A condition of forming the carbon-group-material layer 23 by amicrowave plasma CVD method may be the same condition as that shown inTable 1.

[0333] [Step-860]

[0334] For exposing the opening end portion of the gate electrode 13,preferably, the side wall surface of the second opening portion 14Bformed in the insulating layer 12 is allowed to recede by isotropicetching. In this manner, the field emission device shown in FIG. 12B canbe completed. Otherwise, there can be obtained an electron emittingapparatus which is constituted of the electrically conductive layer(corresponding to the cathode electrode 11 in Example 8) on the surfaceof which the selective-growth region 20 is formed, and the electronemitting portion comprising the carbon-group-material layer 23 formed onthe selective-growth region 20. The above isotropic etching can becarried out by a dry etching method using a radical as a main etchingspecies such as a chemical dry etching method, or a wet etching methodusing an etching solution. As an etching solution, for example, therecan be used a 49% hydrofluoric acid aqueous solution/pure water mixturehaving a 49% hydrofluoric acid aqueous solution:pure water mixing ratioof 1:100 (volume ratio).

[0335] [Step-870]

[0336] Then, a display is assembled in the same manner as in [Step-130]in Example 1.

[0337] In the display having the above constitution, the electronemitting portion of the field emission device comprises the flatcarbon-group-material layer 23 which is exposed in the bottom portion ofthe second opening portion 14B and has a low work function, and thefabrication thereof does not require such complicated and advancedfabrication techniques as have been required concerning the conventionalSpindt type field emission device. Moreover, the etching of thecarbon-group-material layer 23 is no longer required. When the area ofthe effective field of a display increases and when the number ofelectron emitting portions to be formed increases accordingly to a greatextent, the electron emission efficiency of the electron emittingportions can be rendered uniform throughout the entire region of theeffective field, and there can be realized a display which is remarkablyfree of non-uniformity in brightness and has high image quality.

[0338] When [Step-220] and [Step-230] in Example 2 are carried out in[Step-850] or the step of forming a carbon-group-material layer inExamples 9 to 16 to be described later, the electron emitting apparatushaving a selective-growth region according to the second aspect of thepresent invention, the field emission device having a selective-growthregion according to the fifth-A aspect of the present invention and thedisplay having a selective-growth region according to the fifth-A aspectof the present invention can be obtained, and it comes to mean that themanufacturing method of a field emission device and the manufacturingmethod of a display according to the fifth-A aspect/fifth-A(2) aspect ofthe present invention are carried out.

[0339] Alternatively, when [Step-320] and [Step-330] in Example 3 arecarried out, the electron emitting apparatus having a selective-growthregion according to the third aspect of the present invention, the fieldemission device having a selective-growth region according to thesixth-A aspect of the present invention and the display having aselective-growth region according to the sixth-A aspect of the presentinvention can be obtained, and it comes to mean that the manufacturingmethod of a field emission device and the manufacturing method of adisplay according to the sixth-A aspect/sixth-A(2) aspect of the presentinvention are carried out.

EXAMPLE 9

[0340] Example 9 is directed to variants of the manufacturing method ofa field emission device and the manufacturing method of a displayexplained in Example 8. In the manufacturing method of a field emissiondevice and the manufacturing method of a display explained in Example 8,if the carbon-group-material layer 23 is not formed immediately afterthe metal particles 21 are allowed to adhere onto the cathode electrodeportion, the surface of the metal particles 21 are naturally oxidized tomake it difficult to form the carbon-group-material layer 23 in somecases. In Example 9, after the metal particles 21 are allowed to adhereonto the portion of the cathode electrode 11 in which theselective-growth region 20 is to be formed, a metal oxide (so-callednatural oxide film) on the surface of each metal particle 21 is removed.The metal oxide on the surface of each metal particle can be removed byplasma reduction treatment or washing.

[0341] The electron emitting apparatus, the field emission device andthe display to be produced in Example 9 or any one of Examples 10 to 16to be explained later are structurally the same as those in Example 8,so that detailed explanations thereof are omitted. The manufacturingmethod of an electron emitting apparatus, the manufacturing method of afield emission device and the manufacturing method of a display inExample 9 will be explained below.

[0342] [Step-900]

[0343] In the same manner as in [Step-800] to [Step-830] in Example 8, acathode electrode 11 is formed on a supporting member 10 made, forexample, of a glass substrate; then, an insulating layer 12 is formed onthe supporting member 10 and the cathode electrode 11; then, a gateelectrode 13 having a first opening portion 14A is formed on theinsulating layer 12; and then, a second opening portion 14Bcommunicating with the first opening portion 14A formed in the gateelectrode 13 is formed in the insulating layer 12.

[0344] [Step-910]

[0345] Then, a mask layer 116 is formed so as to expose the surface ofthe cathode electrode 11 in a central portion of the bottom portion ofthe second opening portion 14B in the same manner as in [Step-840] inExample 8. Then, metal particles are allowed to adhere onto the masklayer 116 and the exposed surface of the cathode electrode 11.Specifically, a dispersion prepared by dispersing molybdenum (Mo) fineparticles in a polysiloxane solution (using isopropyl alcohol as asolvent) is applied to the entire surface by a spin coating method, toform a layer composed of the solvent and the metal particles on thecathode electrode portion. Then, the mask layer 116 is removed, and thesolvent is fully removed by heating the above layer up to approximately400° C., to retain the metal particles 21 on the exposed surface of thecathode electrode 11, whereby the selective-growth region 20 can beobtained.

[0346] [Step-920]

[0347] Then, the metal oxide (natural oxide film) on the surface of eachmetal particle 21 is removed by plasma reduction treatment (microwaveplasma treatment) under the condition shown in Table 9. Otherwise, themetal oxide (natural oxide film) on the surface of each metal particle21 can be removed, for example, with a 50% hydrofluoric acid aqueoussolution/pure water mixture having a 50% hydrofluoric acid aqueoussolution:pure water mixing ratio of 1:49 (volume ratio).

[0348] [Step-930]

[0349] Then, the carbon-group-material layer 23 having a thickness ofapproximately 0.2 μm is formed on the selective-growth region 20, toobtain an electron emitting portion in the same manner as in [Step-850]in Example 8. A condition of forming the carbon-group-material layer 23according to a microwave plasma CVD method may be the same condition asthat shown in Table 1.

[0350] [Step-940]

[0351] Then, a field emission device as shown in FIG. 12B can beobtained in the same manner as in [Step-860] in Example 8. Otherwise,there can be obtained an electron emitting apparatus which isconstituted of the electrically conductive layer (corresponding to thecathode electrode 11 in Example 9) on the surface of which theselective-growth region 20 is formed, and the electron emitting portioncomprising the carbon-group-material layer 23 formed on theselective-growth region 20. Further, a display is assembled in the samemanner as in [Step-130] in Example 1.

EXAMPLE 10

[0352] Example 10 is also directed to variants of the manufacturingmethods explained in Example 8. In the manufacturing method of a fieldemission device and the manufacturing method of a display explained inExample 8, the metal particles 21 are allowed to adhere onto the cathodeelectrode portion. In Example 10, the step of allowing the metalparticles to adhere onto the cathode electrode portion comprises thesteps of allowing metal compound particles containing a metal atomconstituting the metal particles to adhere onto the cathode electrodeportion, and then, heating the metal compound particles to decomposethem, to obtain the selective-growth region constituted of the surfaceof the cathode electrode onto which surface the metal particles adhere.Specifically, a layer composed of a solvent and the metal compoundparticles (copper iodide in Example 10) is formed on the cathodeelectrode portion, then the solvent is removed to retain the metalcompound particles, and the metal compound particles (copper iodideparticles) are decomposed by heating, to obtain the selective-growthregion constituted of that portion of the cathode electrode whichportion has a surface onto which the metal particles (copper particles)adhere. The manufacturing method of an electron emitting apparatus, themanufacturing method of a field emission device and the manufacturingmethod of a display in Example 9 will be explained below.

[0353] [Step-1000]

[0354] In the same manner as in [Step-800] to [Step-830] in Example 8, acathode electrode 11 is formed on a supporting member 10 made, forexample, of a glass substrate; then, an insulating layer 12 is formed onthe supporting member 10 and the cathode electrode 11; then, a gateelectrode 13 having a first opening portion 14A is formed on theinsulating layer 12; and then, a second opening portion 14Bcommunicating with the first opening portion 14A formed in the gateelectrode 13 is formed in the insulating layer 12.

[0355] [Step-1010]

[0356] Then, a mask layer 116 is formed so as to expose the surface ofthe cathode electrode 11 in a central portion of the bottom portion ofthe second opening portion 14B in the same manner as in [Step-840] inExample 8. Then, metal particles are allowed to adhere onto the exposedsurface of the cathode electrode 11. Specifically, a dispersion preparedby dispersing copper iodide fine particles in a polysiloxane solution isapplied to the entire surface by a spin coating method in the samemanner as in Example 8, to form a layer composed of the solvent and themetal compound particles (copper iodide particles) on the cathodeelectrode portion. Then, the mask layer 116 is removed, and heattreatment is carried out at 400° C. to fully remove the solvent, topyrolyze the copper iodide and to precipitate the metal particles(copper particles) 21 on the exposed surface of the cathode electrode11, whereby the selective-growth region 20 can be obtained.

[0357] [Step-1020]

[0358] Then, the carbon-group-material layer 23 having a thickness ofapproximately 0.2 μm is formed on the selective-growth region 20 in thesame manner as in [Step-850] in Example 8, to obtain an electronemitting portion. Then, a field emission device as shown in FIG. 12B canbe obtained in the same manner as in [Step-860] in Example 8. Otherwise,there can be obtained an electron emitting apparatus which isconstituted of the electrically conductive layer (corresponding to thecathode electrode 11 in Example 10) on the surface of which theselective-growth region 20 is formed, and the electron emitting portioncomprising the carbon-group-material layer 23 formed on theselective-growth region 20. Further, a display is assembled in the samemanner as in [Step-130] in Example 1.

[0359] Further, the metal oxide (natural oxide film) on the surface ofeach metal particle 21 may be removed in the same manner as in[Step-920] in Example 9.

EXAMPLE 11

[0360] Example 11 is also directed to variants of the manufacturingmethods explained in Example 8. In the manufacturing methods explainedin Example 8, the metal particles 21 are allowed to adhere onto thecathode electrode portion. In Example 11, the step of forming theselective-growth region comprises the steps of forming a mask layer soas to expose the surface of the cathode electrode in the bottom portionof the second opening portion and then forming a metal thin layercomposed of titanium (Ti) on the mask layer and the exposed surface ofthe cathode electrode by a sputtering method. The manufacturing methodof an electron emitting apparatus, the manufacturing method of a fieldemission device and the manufacturing method of a display in Example 11will be explained below.

[0361] [Step-1100]

[0362] In the same manner as in [Step-800] to [Step-830] in Example 8, acathode electrode 11 is formed on a supporting member 10 made, forexample, of a glass substrate; then, an insulating layer 12 is formed onthe supporting member 10 and the cathode electrode 11; then, a gateelectrode 13 having a first opening portion 14A is formed on theinsulating layer 12; and then, a second opening portion 14Bcommunicating with the first opening portion 14A formed in the gateelectrode 13 is formed in the insulating layer 12.

[0363] [Step-1110]

[0364] Then, a mask layer 116 is formed so as to expose the surface ofthe cathode electrode 11 in a central portion of the bottom portion ofthe second opening portion 14B in the same manner as in [Step-840] inExample 8. Then, a metal thin layer 22 is formed on the mask layer 116and the exposed surface of the cathode electrode 11 by a sputteringmethod under the condition shown in Table 6, and then the mask layer 116is removed (see FIG. 13A). In this manner, there can be obtained theselective-growth region 20 constituted of that portion of the cathodeelectrode which portion has the surface on which the metal thin layer 22is formed.

[0365] [Step-1120]

[0366] Then, the carbon-group-material layer 23 having a thickness ofapproximately 0.2 μm is formed on the selective-growth region 20 in thesame manner as in [Step-850] in Example 8, to obtain an electronemitting portion (see FIG. 13B). Then, the field emission device can becompleted in the same manner as in [Step-860] in Example 8. Otherwise,there can be obtained an electron emitting apparatus which isconstituted of the electrically conductive layer (corresponding to thecathode electrode 11 in Example 11) on the surface of which theselective-growth region 20 is formed, and the electron emitting portioncomprising the carbon-group-material layer 23 formed on theselective-growth region 20. Further, a display is assembled in the samemanner as in [Step-130] in Example 1.

[0367] The metal oxide (natural oxide film) on the surface of the metalthin layer 22 may be removed in the same manner as in [Step-920] inExample 9. Further, there may be employed a constitution in which, inthe same manner as in Example 10, a metal compound thin layer is formedon the surface of the cathode electrode 11 which portion is positionedin the bottom portion of the second opening portion 14B, by a sputteringmethod, and the metal compound thin layer is pyrolyzed to form theselective-growth region 20 composed of the metal thin layer formed onthe surface of the cathode electrode. Further, the metal thin layer maybe formed by an MOCVD method.

EXAMPLE 12

[0368] Example 12 is also directed to variants of the manufacturingmethods explained in Example 8. In Example 12, the selective-growthregion is composed of an organometallic compound thin layer, morespecifically, composed of a complex compound of nickel acetylacetonate.In Example 12, further, the step of forming the organometallic compoundthin layer on the cathode electrode portion comprises the step ofapplying an organometallic compound solution onto the cathode electrode.The manufacturing method of an electron emitting apparatus, themanufacturing method of a field emission device and the manufacturingmethod of a display in Example 12 will be explained below.

[0369] [Step-1200]

[0370] In the same manner as in [Step-800] to [Step-830] in Example 8, acathode electrode 11 is formed on a supporting member 10 made, forexample, of a glass substrate; then, an insulating layer 12 is formed onthe supporting member 10 and the cathode electrode 11; then, a gateelectrode 13 having a first opening portion 14A is formed on theinsulating layer 12; and then, a second opening portion 14Bcommunicating with the first opening portion 14A formed in the gateelectrode 13 is formed in the insulating layer 12.

[0371] [Step-1210]

[0372] Then, a mask layer 116 is formed so as to expose the surface ofthe cathode electrode 11 in a central portion of the bottom portion ofthe second opening portion 14B in the same manner as in [Step-840] inExample 8. Then, a layer composed of an organometallic compound solutioncontaining nickel acetylacetonate is formed on the mask layer 116 andthe exposed surface of the cathode electrode 11 by a spin coatingmethod, the applied organometallic compound solution is dried and thenthe mask layer 116 is removed, whereby there can be obtained theselective-growth region 20 composed of the organometallic compound thinlayer which is formed on the portion of the cathode electrode whichportion is exposed in the bottom portion of the opening portions 14A and14B and which is composed of nickel acetylacetonate.

[0373] [Step-1220]

[0374] Then, the carbon-group-material layer 23 having a thickness ofapproximately 0.2 μm is formed on the selective-growth region 20 in thesame manner as in [Step-850] in Example 8, to obtain an electronemitting portion. Then, the field emission device can be completed inthe same manner as in [Step-860] in Example 8. Otherwise, there can beobtained an electron emitting apparatus which is constituted of theelectrically conductive layer (corresponding to the cathode electrode 11in Example 12) on the surface of which the selective-growth region 20 isformed, and the electron emitting portion comprising thecarbon-group-material layer 23 formed on the selective-growth region 20.Further, a display is assembled in the same manner as in [Step-130] inExample 1.

[0375] In Example 12, after the organometallic compound thin layer isformed, the metal oxide (natural oxide film) on the surface of theorganometallic compound thin layer may be also removed in the samemanner as in [Step-920] in Example 9.

EXAMPLE 13

[0376] Example 13 is also directed to variants of the manufacturingmethods explained in Example 8 and further those of Example 12. InExample 13, the selective-growth region is composed of an organometalliccompound thin layer, more specifically, is composed of a complexcompound of nickel acetylacetonate. In Example 13, the step of formingthe organometallic compound thin layer on the cathode electrode portioncomprises the steps of sublimating an organometallic compound and thendepositing such an organometallic compound on the cathode electrode. Themanufacturing method of an electron emitting apparatus, themanufacturing method of a field emission device and the manufacturingmethod of a display in Example 13 will be explained below.

[0377] [Step-1300]

[0378] In the same manner as in [Step-800] to [Step-830] in Example 8, acathode electrode 11 is formed on a supporting member 10 made, forexample, of a glass substrate; then, an insulating layer 12 is formed onthe supporting member 10 and the cathode electrode 11; then, a gateelectrode 13 having a first opening portion 14A is formed on theinsulating layer 12; and then, a second opening portion 14Bcommunicating with the first opening portion 14A formed in the gateelectrode 13 is formed in the insulating layer 12.

[0379] [Step-1310]

[0380] Then, a mask layer 116 is formed so as to expose the surface ofthe cathode electrode 11 in a central portion of the bottom portion ofthe second opening portion 14B in the same manner as in [Step-840] inExample 8. Then, an organometallic compound thin layer composed ofnickel acetylacetonate is formed on the mask layer 116 and the exposedsurface of the cathode electrode 11. Specifically, there is provided afilm-forming apparatus having a reaction chamber and a sublimatingchamber connected to the reaction chamber through a heatable tubing. Thesupporting member is transported into the reaction chamber, and then thereaction chamber is adjusted to have an inert gas atmosphere. Then, thenickel acetylacetonate is sublimated in the sublimation chamber, and thesublimated nickel acetylacetonate is sent to the reaction chambertogether with a carrier gas. In the reaction chamber, an organometalliccompound thin layer containing nickel acetylacetonate is deposited onthe mask layer 116 and the exposed surface of the cathode electrode 11.The supporting member 10 can have a room temperature. Then, the masklayer 116 is removed to give the selective-growth region 20 composed ofthe organometallic compound thin layer which is formed on the portion ofthe cathode electrode 11 which portion is exposed in the bottom portionof the opening portions 14A and 14B and which is composed of nickelacetylacetonate.

[0381] [Step-1320]

[0382] Then, the carbon-group-material layer 23 having a thickness ofapproximately 0.2 μm is formed on the selective-growth region 20 in thesame manner as in [Step-850] in Example 8, to obtain an electronemitting portion. Then, the field emission device can be completed inthe same manner as in [Step-860] in Example 8. Otherwise, there can beobtained an electron emitting apparatus which is constituted of theelectrically conductive layer (corresponding to the cathode electrode 11in Example 13) on the surface of which the selective-growth region 20 isformed, and the electron emitting portion comprising thecarbon-group-material layer 23 formed on the selective-growth region 20.Further, a display is assembled in the same manner as in [Step-130] inExample 1.

[0383] In Example 13, after the organometallic compound thin layer isformed, the metal oxide (natural oxide film) on the surface of theorganometallic compound thin layer may be also removed in the samemanner as in [Step-920] in Example 9.

EXAMPLE 14

[0384] Example 14 is also directed to variants of the manufacturingmethods explained in Example 8. In Example 14, the selective-growthregion composed of a metal thin layer is formed on the surface of thecathode electrode by a plating method. The manufacturing method of anelectron emitting apparatus, the manufacturing method of a fieldemission device and the manufacturing method of a display in Example 14will be explained below.

[0385] [Step-1400]

[0386] In the same manner as in [Step-800] to [Step-830] in Example 8, acathode electrode 11 is formed on a supporting member 10 made, forexample, of a glass substrate; then, an insulating layer 12 is formed onthe supporting member 10 and the cathode electrode 11; then, a gateelectrode 13 having a first opening portion 14A is formed on theinsulating layer 12; and then, a second opening portion 14Bcommunicating with the first opening portion 14A formed in the gateelectrode 13 is formed in the insulating layer 12.

[0387] [Step-1410]

[0388] Then, a mask layer 116 is formed so as to expose the surface ofthe cathode electrode 11 in a central portion of the bottom portion ofthe second opening portion 14B in the same manner as in [Step-840] inExample 8. Then, the selective-growth region 20 composed of a metal thinlayer is formed on the exposed surface of the cathode electrode 11 by aplating method. Specifically, the supporting member is immersed in azinc plating solution bath, and the selective-growth region 20constituted of a metal thin layer composed of zinc (Zn) is formed on theexposed surface of the cathode electrode 11 by a zinc plating method inwhich the cathode electrode 11 is connected to a cathode side and nickelas an anticathode is connected to an anode side. For reliably preventthe deposition of a zinc layer on the gate electrode, it is preferred toconnect the gate electrode 13 to the anode side. Then, the mask layer116 is removed using an organic solvent such as acetone, to give theselective-growth region 20 which is constituted of a metal thin layercomposed of zinc (Zn) and is formed on the portion of the cathodeelectrode 11 which portion is exposed in the bottom portion of theopening portions 14A and 14B. If the zinc plating solution bath isreplaced with a tin plating solution bath, there can be obtained aselective-growth region 20 constituted of a metal thin layer composed oftin (Sn).

[0389] [Step-1420]

[0390] Then, the carbon-group-material layer 23 having a thickness ofapproximately 0.2 μm is formed on the selective-growth region 20, toobtain an electron emitting portion in the same manner as in [Step-850]in Example 8. A condition of forming the carbon-group-material layer 23according to a microwave plasma CVD method may be the same condition asthat shown in Table 1.

[0391] [Step-1430]

[0392] Then, the field emission device can be completed in the samemanner as in [Step-860] in Example 8. Otherwise, there can be obtainedan electron emitting apparatus which is constituted of the electricallyconductive layer (corresponding to the cathode electrode 11 in Example14) on the surface of which the selective-growth region 20 is formed,and the electron emitting portion comprising the carbon-group-materiallayer 23 formed on the selective-growth region 20. Further, a display isassembled in the same manner as in [Step-130] in Example 1.

[0393] In Example 14, after the metal thin layer is formed, the metaloxide (natural oxide film) on the surface of the metal thin layer may beremoved in the same manner as in [Step-920] in Example 9.

EXAMPLE 15

[0394] Example 15 is a variant of Example 14. In Example 15, aconvexo-concave shape is formed in the surface of the selective-growthregion formed on the portion of the cathode electrode 11 which portionis exposed in the bottom portion of the opening portions 14A and 14B. Asa result, the carbon-group-material layer formed thereon hasprotrusions, so that a field emission device having high electronemission efficiency can be obtained. The manufacturing method of anelectron emitting apparatus, the manufacturing method of a fieldemission device and the manufacturing method of a display in Example 15will be explained below.

[0395] [Step-1500]

[0396] In the same manner as in [Step-1400] to [Step-1410] in Example14, a cathode electrode 11 is formed on a supporting member 10 made, forexample, of a glass substrate; then, an insulating layer 12 is formed onthe supporting member 10 and the cathode electrode 11; then, a gateelectrode 13 having a first opening portion 14A is formed on theinsulating layer 12; and then, a second opening portion 14Bcommunicating with the first opening portion 14A formed in the gateelectrode 13 is formed in the insulating layer 12. A mask layer 116 isthen formed so as to expose the surface of the cathode electrode 11 in acentral portion of the bottom portion of the second opening portion 14Bin the same manner as in [Step-840] in Example 8. Then, aselective-growth region 20 constituted of a metal thin layer composed ofzinc (Zn) is formed on the exposed surface of the cathode electrode 11by a plating method.

[0397] [Step-1510]

[0398] Then, the supporting member 10 is immersed in a 5% sodiumhydroxide aqueous solution, to etch the surface of the selective-growthregion 20 constituted of the metal thin layer composed of zinc (Zn),whereby a convexo-concave shape is formed in the surface of theselective-growth region 20.

[0399] [Step-1520]

[0400] Then, the carbon-group-material layer 23 having a thickness ofapproximately 0.2 μm is formed on the selective-growth region 20, toobtain an electron emitting portion in the same manner as in [Step-850]in Example 8. A condition of forming the carbon-group-material layer 23according to a microwave plasma CVD method may be the same condition asthat shown in Table 1.

[0401] [Step-1530]

[0402] Then, the field emission device can be completed in the samemanner as in [Step-860] in Example 8. Otherwise, there can be obtainedan electron emitting apparatus which is constituted of the electricallyconductive layer (corresponding to the cathode electrode 11 in Example15) on the surface of which the selective-growth region 20 is formed,and the electron emitting portion comprising the carbon-group-materiallayer 23 formed on the selective-growth region 20. Further, a display isassembled in the same manner as in [Step-130] in Example 1.

[0403] In Example 15, Further, for forming (etching) the convexo-concaveshape in the surface of the selective-growth region 20, not only asodium hydroxide aqueous solution is used, but also diluted hydrochloricacid, diluted sulfuric acid or diluted nitric acid may be used dependingupon materials constituting the selective-growth region 20.

[0404] In Example 15, after the metal thin layer is formed, the metaloxide (natural oxide film) on the surface of the metal thin layer may beremoved in the same manner as in [step-920] in Example 9.

EXAMPLE 16

[0405] Example 16 is also directed to variants of the manufacturingmethods explained in Example 8. In Example 16, the selective-growthregion composed of a metal thin layer is formed on the surface of thecathode electrode by a method in which an organometallic compound ispyrolyzed. The manufacturing method of an electron emitting apparatus,the manufacturing method of a field emission device and themanufacturing method of a display in Example 16 will be explained below.

[0406] [Step-1600]

[0407] In the same manner as in [Step-800] to [Step-830] in Example 8, acathode electrode 11 is formed on a supporting member 10 made, forexample, of a glass substrate; then, an insulating layer 12 is formed onthe supporting member 10 and the cathode electrode 11; then, a gateelectrode 13 having a first opening portion 14A is formed on theinsulating layer 12; and then, a second opening portion 14Bcommunicating with the first opening portion 14A formed in the gateelectrode 13 is formed in the insulating layer 12.

[0408] [Step-1610]

[0409] Then, a mask layer 116 is formed so as to expose the surface ofthe cathode electrode 11 in a central portion of the bottom portion ofthe second opening portion 14B in the same manner as in [Step-840] inExample 8. Then, the selective-growth region 20 composed of a metal thinlayer is formed on the mask layer 116 and the exposed surface of thecathode electrode 11 by a method in which nickel acetylacetonate ispyrolyzed. Specifically, there is provided a film-forming apparatushaving a reaction chamber and a sublimating chamber connected to thereaction chamber through a heatable tubing. The supporting member istransported into the reaction chamber, and then the reaction chamber isadjusted to have an inert gas atmosphere. Then, the nickelacetylacetonate is sublimated in the sublimation chamber, and thesublimated nickel acetylacetonate is sent to the reaction chambertogether with a carrier gas. The supporting member is maintained at aproper temperature in advance. The supporting member is preferablyheated at 50 to 300° C., preferably at 100 to 200° C. In the reactionchamber, a nickel (Ni) layer obtained by the pyrolysis of nickelacetyulacetonate is deposited on the mask layer 116 and the exposedsurface of the cathode electrode 11. Then, the mask layer 116 is removedto give a selective-growth region 20 composed of the metal thin layerwhich is composed of nickel (N) and is formed on the portion of thecathode electrode 11 which portion is exposed in the bottom portion ofthe opening portions 14A and 14B.

[0410] Alternatively, for example, an organometallic compound solutioncontaining zinc (Zn) is applied, by a spin coating method, to the entiresurface of the mask layer 116 and the surface of the cathode electrode11 which surface is exposed in the central portion of the bottom portionof the second opening portion 14B, and the resultant coating isheat-treated in a reducing gas atmosphere, to pyrolyze theorganometallic compound containing zinc and to form a zinc (Zn) layer onthe mask layer 116 and the exposed surface of the cathode electrode 11,whereby the selective-growth region 20 constituted of a metal thin layercomposed of zinc (Zn) can be also obtained.

[0411] [Step-1620]

[0412] Then, the carbon-group-material layer having a thickness ofapproximately 0.2 μm is formed on the selective-growth region 20 in thesame manner as in [Step-850] in Example 8, to obtain an electronemitting portion. A condition of forming the carbon material layer 23according to a microwave plasma CVD method may be the same condition asthat shown in Table 1. Then, the field emission device can be completedin the same manner as in [Step-860] in Example 8. Otherwise, there canbe obtained an electron emitting apparatus which is constituted of theelectrically conductive layer (corresponding to the cathode electrode 11in Example 16) on the surface of which the selective-growth region 20 isformed, and the electron emitting portion comprising thecarbon-group-material layer 23 formed on the selective-growth region 20.Further, a display is assembled in the same manner as in [Step-130] inExample 1.

[0413] In Example 16, after the metal thin layer is formed, the metaloxide (natural oxide film) on the surface of the metal thin layer may beremoved in the same manner as in [Step-920] in Example 9.

EXAMPLE 17

[0414] Example 17 is concerned with the electron emitting apparatushaving a selective-growth region according to the first aspect of thepresent invention, the field emission device having a selective-growthregion according to the fourth aspect of the present invention, thedisplay having a selective-growth region according to the fourth aspectof the present invention, the manufacturing method of a field emissiondevice according to the fourth (1) aspect of the present inventionincluding the step of forming a selective-growth region, and themanufacturing method of a display according to the fourth (1) aspect ofthe present invention including the step of forming a selective-growthregion.

[0415]FIG. 15 shows a schematic partial end view of the field emissiondevice or the electron emitting apparatus of Example 17. The fieldemission device also comprises a cathode electrode 11 formed on asupporting member 10 and a gate electrode 13 which is formed above thecathode electrode 11 and has a first opening portion 14A. The fieldemission device further has a selective-growth region 20 formed on aportion of the cathode electrode 11 which portion is positioned in abottom portion of opening portions 14A and 14B, and an electron emittingportion comprising a carbon-group-material layer 23 formed on theselective-growth region 20. In Example 17, the selective-growth region20 is constituted of metal particles 21 composed of nickel (Ni) whichadheres on the surface of the cathode electrode 11. Differing from thoseof the field emission devices explained in Examples 8 to 16, theselective-growth region 20 extends to reach an interior of an insulatinglayer 12. In some formation state of the selective-growth region 20,however, the selective-growth region 20 may be formed only on theportion of the cathode electrode 11 which portion is positioned in thebottom of the opening portions 14A and 14B like those of the fieldemission devices explained in Examples 8 to 16.

[0416] In the field emission device of Example 17, the insulating layer12 is formed on the supporting member 10 and the cathode electrode 11,the second opening portion 14B communicating with the first openingportion 14A formed in the gate electrode 13 is formed in the insulatinglayer 12, and the carbon-group-material layer 23 is positioned in thebottom portion of the second opening portion 14B.

[0417] The display of Example 17 is substantially similar to the displayshown in FIG. 9, so that a detailed explanation thereof is omitted.

[0418] The manufacturing method of an electron emitting apparatus, themanufacturing method of a field emission device and the manufacturingmethod of a display in Example 17 will be explained below with referenceto FIGS. 14A and 14B and FIG. 15.

[0419] [Step-1700]

[0420] In the same manner as in [Step-110] in Example 1, an electricallyconductive material layer for a cathode electrode is formed on asupporting member 10 made, for example, of a glass substrate, and theelectrically conductive material layer is patterned by known lithographyand a known RIE method, to form the cathode electrode 11 in the form ofa strip on the supporting member 10. The-cathode electrode 11 in theform of a stripe extends leftward and rightward on the paper surface ofthe drawing. The electrically conductive material layer is composed, forexample, of an approximately 0.2 μm thick aluminum (Al) layer formed bya sputtering method.

[0421] [Step-1710]

[0422] Then, the selective-growth region 20 is formed on the surface ofthe cathode electrode 11 in the same manner as in [Step-110] in Example1 (see FIG. 14A).

[0423] [Step-1720]

[0424] Then, the insulating layer 12 is formed on the supporting member10, the cathode electrode 11 and the selective-growth region 20.Specifically, the insulating layer 12 is formed on the entire surface inthe same manner as in [Step-810] in Example 8, and the gate electrode 13having the first opening portion 14A is formed on the insulating layer12 in the same manner as in [Step-820] in Example 8. Then, the secondopening portion 14B communicating with the first opening portion 14Aformed in the gate electrode 13 is formed in the insulating layer 12 inthe same manner as in [Step-830] in Example 8, to expose theselective-growth region 20 in the bottom portion of the second openingportion 14B. In Example 17, the first opening portion 14A and the secondopening portion 14B have a one-to-one correspondence relationship aswell. That is, one second opening portion 14B is formed per firstopening portion 14A. When viewed as a plan view, the first and secondopening portions 14A and 14B have the form, for example, of a circlehaving a diameter of 1 to 30 μm. It is sufficient to form the openingportions 14A and 14B, for example, in the quantity of approximately 1 to3000 per pixel. In this manner, the structure shown in FIG. 14B can beobtained.

[0425] [Step-1730]

[0426] Then, the carbon-group-material layer 23 having a thickness ofapproximately 0.2 μm is formed on the selective-growth region 20 whichportion is exposed in the bottom portion of the second opening portion14B to obtain the electron emitting portion in the same manner as in[Step-120] in Example 1. FIG. 15 shows the thus-obtained state. Acondition of forming the carbon-group-material layer 23 according to amicrowave plasma CVD method may be the same condition as that shown inTable 1.

[0427] [Step-1740]

[0428] For exposing an opening end portion of the gate electrode 13,preferably, the side wall surface of the second opening portion 14Bformed in the insulating layer 12 is allowed to recede by isotropicetching in the same manner as in [Step-860] in Example 8. Then, adisplay is assembled in the same manner as in [Step-130] in Example 1.

[0429] When [Step-220] and [Step-230] in Example 2 are carried out in[Step-1730], the electron emitting apparatus having a selective-growthregion according to the second aspect of the present invention, thefield emission device having a selective-growth region according to thefifth-A aspect of the present invention and the display having aselective-growth region according to the fifth-A aspect of the presentinvention can be obtained, and it comes to mean that the manufacturingmethod of a field emission device and the manufacturing method of adisplay according to the fifth-A aspect/fifth-A(1) aspect of the presentinvention are carried out.

[0430] Alternatively, when [Step-320] and [Step-330] in Example 3 arecarried out in [Step-1730], the electron emitting apparatus having aselective-growth region according to the third aspect of the presentinvention, the field emission device having a selective-growth regionaccording to the sixth-A aspect of the present invention and the displayhaving a selective-growth region according to the sixth-A aspect of thepresent invention can be obtained, and it comes to mean that themanufacturing method of a field emission device and the manufacturingmethod of a display according to the sixth-A aspect/sixth-A(1) aspect ofthe present invention are carried out.

EXAMPLE 18

[0431] Example 18 is concerned with the electron emitting apparatushaving a selective-growth region according to the first aspect of thepresent invention, the field emission device having a selective-growthregion according to the fourth aspect of the present invention, thedisplay having a selective-growth region according to the fourth aspectof the present invention, the manufacturing method of a field emissiondevice according to the seventh (1) aspect of the present inventionincluding the step of forming a selective-growth region, and themanufacturing method of a display according to the seventh (1) aspect ofthe present invention including the step of forming a selective-growthregion.

[0432]FIG. 16 shows a schematic partial end view of the field emissiondevice or electron emitting apparatus of Example 18. Since the fieldemission device has substantially the same structure as that of thefield emission device explained in Example 17, the detailed explanationthereof will be omitted. Further, since the display of Example 18 issubstantially the same display as that shown in FIG. 9, the detailedexplanation thereof will be omitted. Unlike the field emission devicesexplained in Examples 8 to 16, a selective-growth region 20 and acarbon-group-material layer 23 formed thereon extend into an insulatinglayer 12. In some formed state of the selective-growth region 20, theselective-growth region 20 and the carbon-group-material layer 23 formedthereon may be formed only on a portion of the cathode electrode 11positioned in the bottom portion of opening portions 14A and 14B, likethe field emission devices explained in Examples 8 to 16.

[0433] The manufacturing method of an electron emitting apparatus, themanufacturing method of a field emission device and the manufacturingmethod of a display in Example 18 will be explained below with referenceto FIGS. 3A, 3D and 16.

[0434] [Step-1800]

[0435] In the same manner as in [Step-110] in Example 1, an electricallyconductive material layer for a cathode electrode is formed on asupporting member 10 made, for example, of a glass substrate, and theelectrically conductive material layer is patterned by known lithographyand a known RIE method, to form the cathode electrode 11 in the form ofa stripe on the supporting member 10 (See FIG. 3A). The cathodeelectrode 11 in the form of a stripe extends leftward and rightward onthe paper surface of the drawing. The electrically conductive materiallayer is composed, for example, of an approximately 0.2 μm thickaluminum (Al) layer formed by a sputtering method.

[0436] [Step-1810]

[0437] Then, the selective-growth region 20 is formed on the surface ofthe cathode electrode 11 in the same manner as in [Step-110] in Example1.

[0438] [Step-1820]

[0439] Then, the carbon-group-material layer 23 having a thickness ofapproximately 0.2 μm is formed on the selective-growth region 20 toobtain the electron emitting portion in the same manner as in [Step-120]in Example 1. FIG. 3D shows the thus-obtained state. A condition offorming the carbon-group-material layer 23 according to a microwaveplasma CVD method may be the same condition as that shown in Table 1.

[0440] [Step-1830]

[0441] Then, the gate electrode 13 having the first opening portion 14Ais formed above the carbon-group-material layer 23. Specifically, theinsulating layer 12 is formed on the entire surface in the same manneras in [Step-810] in Example 8, and the gate electrode 13 having thefirst opening portion 14A is formed on the insulating layer 12 in thesame manner as in [Step-820] in Example 8. Then, the second openingportion 14B communicating with the first opening portion 14A formed inthe gate electrode 13 is formed in the insulating layer 12 in the samemanner as in [Step-830] in Example 8, to expose thecarbon-group-material layer 23 in the bottom portion of the secondopening portion 14B. In Example 18, the first opening portion 14A andthe second opening portion 14B have a one-to-one correspondencerelationship as well. That is, one second opening portion 14B is formedper first opening portion 14A. When viewed as a plan view, the first andsecond opening portions 14A and 14B have the form, for example, of acircle having a diameter of 1 to 30 μm. It is sufficient to form theopening portions 14A and 14B, for example, in the quantity ofapproximately 1 to 3000 per pixel. In this manner, the field emissiondevice shown in FIG. 16 can be obtained.

[0442] [Step-1840]

[0443] For exposing an opening end portion of the gate electrode 13,preferably, the side wall surface of the second opening portion 14Bformed in the insulating layer 12 is allowed to recede by isotropicetching in the same manner as in [Step-860] in Example 8. Then, adisplay is assembled in the same manner as in [Step-130] in Example 1.

[0444] When [Step-220] and [Step-230] in Example 2 are carried out in[Step-1820], or when [Step-220] in Example 2 is carried out in[Step-1820] and [Step-1830] is followed by [Step-230] in Example 2, theelectron emitting apparatus having a selective-growth region accordingto the second aspect of the present invention, the field emission devicehaving a selective-growth region according to the fifth-A aspect of thepresent invention and the display having a selective-growth regionaccording to the fifth-A aspect of the present invention can beobtained, and it comes to mean that the manufacturing method of a fieldemission device and the manufacturing method of a display according tothe eighth-A/eighth-A(1) aspect of the present invention are carriedout.

[0445] Alternatively, when [Step-320] and [Step-330] in Example 3 arecarried out in [Step-1820], or when [Step-320] in Example 3 is carriedout in [Step-1820] and [Step-1830] is followed by [Step-330] in Example3, the electron emitting apparatus having a selective-growth regionaccording to the third aspect of the present invention, the fieldemission device having a selective-growth region according to thesixth-A aspect of the present invention and the display having aselective-growth region according to the sixth-A aspect of the presentinvention can be obtained, and it comes to mean that the manufacturingmethod of a field emission device and the manufacturing method of adisplay according to the ninth-A/ninth-A(1) aspect of the presentinvention are carried out.

[0446] In Example 18 or 19, after the formation of the opening portion14A and 14B, the metal oxide (natural oxide film) on the surface of eachmetal particle or on the surface of the metal thin layer in the exposedselective-growth region 20 may be removed as described in [Step-920] inExample 9. There may be employed a constitution in which the metalliccompound particles are allowed to adhere or the metallic compound thinlayer is formed, and then the metallic compound particles or themetallic compound thin layer is pyrolyzed to obtain a selective-growthregion 20 composed of the metal particles adhering onto the surface ofthe cathode electrode or a metal thin layer formed thereon in the samemanner as in Example 10.

[0447] Further, in Example 17 or 18, the step of forming theselective-growth region may comprise the steps of forming a mask layerso as to expose the surface of the cathode electrode in a centralportion of the bottom portion of the second opening portion and forminga metal thin layer on the mask layer and the exposed surface of thecathode electrode by a sputtering method in the same manner as inExample 11. Otherwise, the step of forming the selective-growth regionmay comprise the step of forming, on the cathode electrode, a layer froman organometallic compound solution, or may comprise the steps ofsublimating an organometallic compound and then depositing such anorganometallic compound on the cathode electrode in the same manner asin Example 12 or Example 13. Further, the selective-growth regioncomposed of a metal thin layer may be formed on the surface of thecathode electrode by a plating method in the same manner as in Example14 and Example 15 and the selective-growth region composed of a metalthin layer may be formed on the surface of the cathode electrode by amethod in which an organometallic compound is pyrolyzed in the samemanner as in Example 16.

EXAMPLE 19

[0448] Example 19 is concerned with the electron emitting apparatusaccording to the second-B aspect of the present invention, themanufacturing method of an electron emitting apparatus according to thesecond-B aspect of the present invention, the field emission deviceaccording to the fifth-B aspect of the present invention, themanufacturing method of a field emission device according to the fifth-Baspect, the display according to the fifth-B aspect and themanufacturing method of a display according to the fifth-B aspect.

[0449] The display of Example 19 has substantially the same constitutionas that of the display of Example 5 having a schematic partial end viewshown in FIG. 7, so that the detailed explanation thereof will beomitted.

[0450]FIG. 18B shows a basic constitution of the field emission deviceor electron emitting apparatus in Example 19. The field emission deviceor electron emitting apparatus comprises a cathode electrode(corresponding to an electrically conductive layer) 11 formed on asupporting member 10, and a gate electrode 13 that is formed above thecathode electrode 11 and has an opening portion (first opening portion14A). The field emission device or electron emitting apparatus furtherhas an electron emitting portion 15 comprising a carbon-group-materiallayer 23 formed on that portion of the cathode electrode 11 whichportion is positioned in the bottom portion of the first opening portion14A. Further, an insulating layer 12 is formed on the supporting member10 and the cathode electrode 11, and a second opening portion 14B isformed through the insulating layer 12 and communicates with the firstopening portion 14A formed through the gate electrode 13. In Example 19,the electron emitting portion 15 comprises a matrix 25 and carbonnano-tube structures (specifically, carbon-nano-tubes 26) embedded inthe matrix 25 such that the top end portions thereof are projected. Thematrix 25 is formed of water glass. A fluoride-carbide-containing thinfilm 24 is formed on the surface of the carbon-group-material layer 23,and the fluoride-carbide-containing thin film 24 is a film formed from afluorine-containing hydrocarbon gas.

[0451] The manufacturing method of the electron emitting apparatus, themanufacturing method of the field emission device and the manufacturingmethod of the display in Example 19 will be explained below withreference to FIGS. 17A and 17B and FIGS. 18A and 18B.

[0452] [Step-1900]

[0453] First, a stripe-shaped cathode electrode 11 made of anapproximately 0.2 μm thick chromium (Cr) layer is formed on a supportingmember 10 made, for example, of a glass substrate, for example, by asputtering method and an etching technique.

[0454] [Step-1910]

[0455] Then, a dispersion of carbon nano-tube structures in an inorganicbinder material made of water glass is applied to a predetermined regionof the cathode electrode 11 by a screen printing method, the solvent isremoved, and the binder material is fired, whereby the electron emittingportion 15 can be obtained (see FIG. 17A). As a firing condition, thefiring can be carried out, for example, in dry atmosphere at 400° C. for30 minutes. The carbon-nano-tubes are prepared by an arc dischargemethod and have an average diameter of 30 nm and an average length of 1μm.

[0456] [Step-1920]

[0457] Then, an insulating layer 12 is formed on the supporting member10, the cathode electrode 11 and the electron emitting portion 15.Specifically, the insulating layer 12 having a thickness ofapproximately 1 μm is formed on the entire surface, for example, by aCVD method using TEOS (tetraethoxysilane) as a source gas. Theinsulating layer 12 can be formed under the same condition as that shownin Table 7.

[0458] [Step-1930]

[0459] Then, a stripe-shaped gate electrode 13 is formed on theinsulating layer 12, and further, a mask layer 27 is formed on theinsulating layer 12 and the gate electrode 13. Then, a first openingportion 14A is formed through the gate electrode 13, and further, asecond opening portion 14B communicating with the first opening portion14A formed through the gate electrode 13 is formed through theinsulating layer 12 (see FIG. 17B). When the matrix 25 is constituted ofa water glass 25, for example, the insulating layer 12 can be etchedwithout etching the matrix 25. That is, the etching selection ratiobetween the insulating layer 12 and the matrix 25 is approximatelyinfinite. The carbon nano-tubes 26 are therefore not damaged when theinsulating layer 12 is etched.

[0460] [Step-1940]

[0461] Then, part of the matrix 25 formed of the water glass ispreferably removed with a sodium hydroxide (NaOH) aqueous solution, toobtain the carbon-nano-tubes 26 in a state where the top end portionsthereof are projected from the matrix 25. In this manner, the electronemitting portion 15 having a structure shown in FIG. 18A can beobtained.

[0462] Some or all of the carbon nano-tubes 26 may change in theirsurface state due to the etching of the matrix 25 (for example, oxygenatoms or oxygen molecules are adsorbed to their surfaces), and thecarbon nano-tubes 26 are deactivated with respect of electric fieldemission in some cases. Therefore, it is preferred to subject theelectron-emitting portion 15 to a plasma treatment in a hydrogen gasatmosphere. By the plasma treatment, the electron-emitting portion 15 isactivated, and the efficiency of emission of electrons from theelectron-emitting portion 15 is further improved. Table 11 shows anexample of a plasma treatment condition. TABLE 11 Gas to be used H₂ =100 sccm Source power 1000 W Power to be applied to 50 V supportingmember Reaction pressure 0.1 Pa Substrate temperature 300° C.

[0463] [Step-1950]

[0464] Then, in the same manner as in [Step-230] in Example 2, afluoride-carbide-containing thin film (CF_(x) thin film) 24 is formed onthe surface of the carbon-group-material layer 23 comprising the carbonnano-tubes 26, from a fluorine-containing hydrocarbon gas, thereby toobtain an electron emitting portion 15 comprising thecarbon-group-material layer 23 and the fluoride-carbide-containing thinfilm 24 formed on the surface of the carbon-group-material layer 23 (seeFIG. 18B).

[0465] [Step-1960]

[0466] For exposing an opening end portion of the gate electrode 13,preferably, the side wall surface of the second opening portion 14Bformed in the insulating layer 12 is allowed to recede by isotropicetching in the same manner as in [Step-860] in Example 8. Then, the masklayer 27 is removed.

[0467] [Step-1970]

[0468] Then, a display is assembled in the same manner as in [Step-130]in Example 1.

[0469] When [Step-330] in Example 3 is carried out in [Step-1950], theelectron emitting apparatus according to the third-B aspect of thepresent invention and the manufacturing method thereof, the fieldemission device according the sixth-B aspect of the present inventionand the display according to the sixth-B aspect of the present inventioncan be obtained, and it comes to mean that the manufacturing method of afield emission device and the manufacturing method of a displayaccording to the sixth-B aspect of the present invention are carriedout.

[0470] Alternatively, when [Step-1900], [Step-1910], [Step-1940],[Step-1950] and [Step-1970] are carried out, there are obtained theelectron emitting apparatus according to the second-B aspect of thepresent invention and the manufacturing method thereof, the fieldemission device according to the second-B aspect of the presentinvention and the manufacturing method thereof, and the displayaccording to the second-B aspect of the present invention and themanufacturing method thereof.

[0471] Alternatively, when [Step-1900], [Step-1910], [Step-1940],[Step-330] and [Step-1970] are carried out, there can be obtained theelectron emitting apparatus according to the third-B aspect of thepresent invention and the manufacturing method thereof, the fieldemission device according to the third-B aspect of the present inventionand the manufacturing method thereof, and the display according to thethird-B aspect of the present invention and the manufacturing methodthereof.

[0472] Alternatively, when [Step-1800], [Step-1910], [Step-1830],[Step-1940], [Step-1950] and [Step-1840] are carried out, the electronemitting apparatus and the display according to the fifth-B aspect ofthe present invention can be obtained, and it comes to mean that themanufacturing method of a field emission device according to theeighth-B aspect of the present invention and the manufacturing method ofa display according to the eighth-B aspect of the present invention arecarried out.

[0473] Alternatively, when [Step-1800], [Step-1910], (Step-1830],[Step-1940], [Step-330] and [Step-1840] are carried out, the electronemitting apparatus and the display according to the sixth-B aspect ofthe present invention can be obtained, and it comes to mean that themanufacturing method of a field emission device according to the ninth-Baspect of the present invention and the manufacturing method of adisplay according to the ninth-B aspect of the present invention arecarried out.

EXAMPLE 20

[0474] Example 20 is concerned with the electron emitting apparatusaccording to the second-B aspect of the present invention, themanufacturing method of an electron emitting apparatus according to thesecond-C aspect of the present invention, the field emission deviceaccording to the fifth-B aspect of the present invention, themanufacturing method of a field emission device according to the fifth-Caspect of the present invention, the display according to the fifth-Baspect of the present invention, and the manufacturing method of adisplay according to the fifth-C aspect of the present invention.

[0475] The electron emitting apparatus, the field emission device andthe display in Example 20 have substantially the same structures asthose of the electron emitting apparatus and the field emission devicehaving a schematic partial end view shown in FIG. 18B in Example 19 andof the display having a schematic partial end view shown in FIG. 7 inExample 5, so that the detailed explanations thereof will be omitted. InExample 20, the electron emitting portion 15 comprises a matrix 25 andcarbon nano-tube structures (specifically, carbon-nano-tubes 26)embedded in the matrix 25 in a state where the top end portions thereofare projected, and the matrix 25 is made of a metal oxide havingelectrical conductivity (specifically, indium-tin oxide, ITO). Afluoride-carbide-containing thin film 24 is formed on the surface of acarbon-group-material layer 23, and the fluoride-carbide-containing thinfilm 24 is a film formed from a fluorine-containing hydrocarbon gas.

[0476] The manufacturing method of the field emission device will beexplained below with reference again to FIGS. 17A and 17B and FIGS. 18Aand 18B.

[0477] [Step-2000]

[0478] First, a stripe-shaped cathode electrode 11 made of anapproximately 0.2 μm thick chromium (Cr) layer is formed on a supportingmember 10 made, for example, of a glass substrate, for example, by asputtering method and an etching technique.

[0479] [Step-2010]

[0480] Then, a metal compound solution consisting of an organic acidmetal compound in which the carbon nano-tube structures are dispersed isapplied onto the cathode electrode 11, for example, by a spray method.Specifically, a metal compound solution shown in Table 12 is used. Inthe metal compound solution, the organic tin compound and the organicindium compound are in a state where they are dissolved in an acid (forexample, hydrochloric acid, nitric acid or sulfuric acid). The carbonnano-tube is produced by an arc discharge method and has an averagediameter of 30 nm and an average length of 1 (m. In the application, thesupporting member is heated to 70-150° (C. Atmospheric atmosphere isemployed as an application atmosphere. After the application, thesupporting member is heated for 5 to 30 minutes to fully evaporate butylacetate off. When the supporting member is heated during the applicationas described above, the applied solution begins to dry before the carbonnano-tubes are self-leveled toward a horizontal direction of the surfaceof the cathode electrode. As a result, the carbon nano-tube can bearranged on the surface of the cathode electrode in a state where thecarbon nano-tube is not in a level position. That is, the carbonnano-tube can be aligned in the direction in which the top portion ofthe carbon nano-tube faces the anode electrode, in other words, thecarbon nano-tube comes close to the normal direction of the supportingmember. The metal compound solution having a composition shown in Table12 may be prepared beforehand, or a metal compound solution containingno carbon nano-tubes may be prepared beforehand and the carbonnano-tubes and the metal compound solution may be mixed before theapplication. For improving dispersibility of the carbon nano-tubes,ultrasonic wave may be applied when the metal compound solution isprepared. TABLE 12 Organic tin compound and 0.1-10 parts by weightorganic indium compound Dispersing agent (sodium 0.1-5 parts by weightdodecylsulfate) Carbon nano-tubes 0.1-20 parts by weight Butyl acetateBalance

[0481] When a solution of an organic tin compound dissolved in an acidis used as an organic acid metal compound solution, tin oxide isobtained as a matrix. When a solution of an organic indium compounddissolved in an acid is used, indium oxide is obtained as a matrix. Whena solution of an organic zinc compound dissolved in an acid is used,zinc oxide is obtained as a matrix. When a solution of an organicantimony compound dissolved in an acid is used, antimony oxide isobtained as a matrix. When a solution of an organic antimony compoundand an organic tin compound dissolved in an acid is used, antimony-tinoxide is obtained as a matrix. Further, when an organic tin compound isused as an organic metal compound solution, tin oxide is obtained as amatrix. When an organic indium compound is used, indium oxide isobtained as a matrix. When an organic zinc compound is used, zinc oxideis obtained as a matrix. When an organic antimony compound is used,antimony oxide is obtained as a matrix. When an organic antimonycompound and an organic tin compound are used, antimony-tin oxide isobtained as a matrix. Alternatively, a solution of metal chloride (forexample, tin chloride or indium chloride) may be used.

[0482] After the metal compound solution is dried, salientconvexo-concave shapes may be formed on the surface of the metalcompound layer in some cases. In such cases, it is desirable to applythe metal compound solution again on the metal compound layer withoutheating the supporting member.

[0483] [Step-2020]

[0484] Then, the metal compound constituted of the organic acid metalcompound is fired, to give an electron emitting portion 15 having thecarbon nano-tubes 26 fixed onto the surface of the cathode electrode 11with the matrix 25 (which is specifically a metal oxide, and morespecifically, ITO) containing metal atoms (specifically, In and Sn)constituting the organic acid metal compound. The firing is carried outin an atmospheric atmosphere at 350 (C. for 20 minutes. Thethus-obtained matrix 25 had a volume resistivity of 5×10⁻⁷ ((m. When theorganic acid metal compound is used as a starting material, the matrix25 made of ITO can be formed at a low firing temperature of as low as350 (C. The organic acid metal compound solution may be replaced with anorganic metal compound solution. When a solution of metal chloride (forexample, tin chloride and indium chloride) is used, the matrix 25 madeof ITO is formed while the tin chloride and indium chloride are oxidizedby the firing.

[0485] [Step-2030]

[0486] Then, a resist layer is formed on the entire surface, and thecircular resist layer having a diameter, for example, of 10 μm isretained above a desired region of the cathode electrode 11. The matrix25 is etched with hydrochloric acid having a temperature of 10 to 60° C.for 1 to 30 minutes, to remove an unnecessary portion of the electronemitting portion. Further, when the carbon nano-tubes still remain in aregion different from the desired region, the carbon nano-tubes areetched by an oxygen plasma etching treatment under a condition shown inTable 13. A bias power may be 0 W, i.e., direct current, while it isdesirable to apply the bias power. The supporting member may be heated,for example, to approximately 80° C. TABLE 13 Apparatus to be used RIEapparatus Gas to be introduced Gas containing oxygen Plasma excitingpower 500 W Bias power 0-150 W Treatment time period at least 10 seconds

[0487] Alternatively, the carbon nano-tubes can be etched by a wetetching treatment under a condition shown in Table 14. TABLE 14 Solutionto be used KMnO₄ Temperature       20-120° C. Treatment time period    10 seconds-20 minutes 

[0488] Then, the resist layer is removed, whereby a structure shown inFIG. 17A can be obtained. It is not necessarily required to retain acircular electron emitting portion having a diameter of 10 μm. Forexample, the electron-emitting portion may be retained on the cathodeelectrode 11.

[0489] The process may be carried out in the order of [Step-2010],[Step-2030] and [Step-2020]. [Step-2040]

[0490] Then, an insulating layer 12 is formed on the supporting member10, the cathode electrode 11 and the electron emitting portion 15.Specifically, the insulating layer 12 having a thickness ofapproximately 1 μm is formed on the entire surface, for example, by aCVD method using TEOS (tetraethoxysilane) as a source gas. Theinsulating layer 12 can be formed under the same condition as that shownin Table 7.

[0491] [Step-2050]

[0492] Then, a stripe-shaped gate electrode 13 is formed on theinsulating layer 12, and further, a mask layer 27 is formed on theinsulating layer 12 and the gate electrode 13. Then, a first openingportion 14A is formed through the gate electrode 13, and further, asecond opening portion 14B communicating with the first opening portion14A formed through the gate electrode 13 is formed through theinsulating layer 12 (see FIG. 17B). When the matrix 25 is constituted ofa metal oxide, for example, ITO, the insulating layer 12 can be etchedwithout etching the matrix 25. That is, the etching selection ratiobetween the insulating layer 12 and the matrix 25 is approximatelyinfinite. The carbon nano-tubes 26 are therefore not damaged when theinsulating layer 12 is etched.

[0493] [Step-2060]

[0494] Then, preferably, part of the matrix 25 is removed under acondition shown in Table 15, to obtain the carbon nano-tubes 26 in astate where top portions thereof are projected from the matrix 25. Inthis manner, the electron emitting portion 15 having a structure shownin FIG. 18A can be obtained. TABLE 15 Etching solution Hydrochloric acidEtching time period     10 seconds-30 seconds Etching temperature       10-60° C. 

[0495] Some or all of the carbon nano-tubes 26 may change in theirsurface state due to the etching of the matrix 25 (for example, oxygenatoms or oxygen molecules or fluorine atoms are adsorbed to theirsurfaces), and the carbon nano-tubes 26 are deactivated with respect ofelectric field emission in some cases. Therefore, it is preferred tosubject the electron emitting portion 15 to a plasma treatment in ahydrogen gas atmosphere. By the plasma treatment, the electron emittingportion 15 is activated, and the efficiency of emission of electronsfrom the electron emitting portion 15 is further improved. A conditionof the plasma treatment may be the same condition as those shown inTable 11.

[0496] [Step-2070]

[0497] Then, in the same manner as in [Step-230] in Example 2, afluoride-carbide-containing thin film (CF_(x) thin film) 24 is formed onthe surface of the carbon-group-material layer 23 comprising the carbonnano-tubes 26, from a fluorine-containing hydrocarbon gas, thereby toobtain an electron emitting portion 15 comprising thecarbon-group-material layer 23 and the fluoride-carbide-containing thinfilm 24 formed on the surface of the carbon-group-material layer 23.

[0498] [Step-2080]

[0499] For exposing an opening end portion of the gate electrode 13,preferably, the side wall surface of the second opening portion 14Bformed in the insulating layer 12 is allowed to recede by isotropicetching in the same manner as in [Step-860] in Example 8. Then, the masklayer 27 is removed. In this manner, the field emission device shown inFIG. 18B can be completed.

[0500] [Step-2090]

[0501] Then, a display is assembled in the same manner as in [Step-130]in Example 1.

[0502] When [Step-330] in Example 3 is carried out in [Step-2070], theelectron emitting apparatus according to the third-C aspect of thepresent invention and the manufacturing method thereof, the fieldemission device according to the sixth-B aspect of the presentinvention, and the display according to the sixth-B aspect of thepresent invention can be obtained, and it comes to mean that themanufacturing method of a field emission device and the manufacturingmethod of a display according to the sixth-C aspect of the presentinvention are carried out.

[0503] Alternatively, when [Step-2000] to [Step-2030], [Step-2060],[Step-2070] and [Step-2090] are carried out, the electron emittingapparatus according to the second-B aspect of the present invention, thefield emission device according to the second-B aspect of the presentinvention and the display according to the second-B aspect of thepresent invention can be obtained, and it comes to mean that themanufacturing method of an electron emitting apparatus according to thesecond-C aspect of the present invention, the manufacturing method of afield emission device according to the second-C aspect of the presentinvention and the manufacturing method of a display according to thesecond-C aspect of the present invention are carried out.

[0504] Alternatively, when [Step-2000] to [Step-2030], [Step-2060],[Step-330] and [Step-2090] are carried out, the electron emittingapparatus according to the third-B aspect of the present invention, thefield emission device according to the third-B aspect of the presentinvention and the display according to the third-B aspect of the presentinvention can be obtained, it comes to mean that the manufacturingmethod of an electron emitting apparatus according to the third-C aspectof the present invention, the manufacturing method of a field emissiondevice according to the third-C aspect of the present invention and themanufacturing method of a display according to the third-C aspect of thepresent invention are carried out.

[0505] Alternatively, when [Step-1800], [Step-2010] to [Step-2030],[Step-1830], [Step-2060], [Step-2070] and [Step-1840] are carried out,the electron emitting apparatus according to the second-B aspect of thepresent invention, the field emission device according to the fifth-Baspect of the present invention and the display according to the fifth-Baspect of the present invention can be obtained, and it comes to meanthat the manufacturing method of an electron emitting apparatusaccording to the second-C aspect of the present invention, themanufacturing method of a field emission device according to theeighth-C aspect of the present invention and the manufacturing method ofa display according to the eighth-C aspect of the present invention arecarried out.

[0506] Alternatively, when [Step-1800], [Step-2010] to (Step-2030],[Step-1830], [Step-2060], [Step-330] and [Step-1840] are carried out,the electron emitting apparatus according to the third-B aspect of thepresent invention, the field emission device according to the sixth-Baspect of the present invention and the display according to the sixth-Baspect of the present invention can be obtained, and it comes to meanthat the manufacturing method of an electron emitting apparatusaccording to the third-C aspect of the present invention, themanufacturing method of a field emission device according to the ninth-Caspect of the present invention and the manufacturing method of adisplay according to the ninth-C aspect of the present invention arecarried out.

[0507] While the present invention has been explained on the basis ofExamples, the present invention shall not be limited thereto. Theconstitutions and structures explained with regard to the anode panel,the cathode panel, the displays and the field emission devices inExamples are given as examples and may be modified as required. Themanufacturing method, various conditions and materials explained withregard to the anode panel, the cathode panel, the displays and the fieldemission devices are given as examples and may be modified as required.Further, the various materials used in the manufacture of the anodepanels and the cathode panels are also given as examples and may bechanged as required. With regard to the display, color displays areexplained as examples, while the display may be a monochromatic display.

[0508] A variant of the “two-electrodes” type display explained inExamples 1 to 4 will be explained below. This display variant has aschematic partial cross-sectional view as shown in FIG. 1. In thedisplay variant, a cathode electrode 11 and an anode electrode 33 havethe form of a stripe and have a structure in which the projection imageof the stripe-shaped cathode electrode 11 and the projection image ofthe stripe-shaped anode electrode 33 cross each other at right angles.Specifically, the cathode electrode 11 extends in the directionperpendicular to the paper surface of FIG. 1, and the anode electrode 33extends rightward and leftward on the paper surface of the drawing. In acathode panel CP of the above display variant, a great number ofelectron emitting portions constituted of a plurality of the above fieldemission devices each are formed in an effective field in the form of atwo-dimensional matrix. It is not required to provide a switchingelement between the cathode electrode and a cathode-electrode controlcircuit 40A.

[0509] In the above display variant, an electric field formed by theanode electrode 33 causes the electron emitting portion 15 to emitelectrons on the basis of a quantum tunnel effect, and the electrons aredrawn to the anode electrode 33 to collide with a phosphor layer 31.That is, the display is driven by a so-called simple matrix method inwhich electrons are emitted from the electron emitting portion 15positioned in an overlap region where the projection images of the anodeelectrode 33 and the cathode electrode 11 overlap (a cathodeelectrode/anode electrode overlap region). Specifically, a relativelynegative voltage is applied to the cathode electrode 11 from thecathode-electrode control circuit 40A, and a relatively positive voltageis applied to the anode electrode 33 from an anode-electrode controlcircuit 42. As a result, electrons are selectively emitted into a vacuumspace from the electron emitting portion 15 positioned in the anodeelectrode/cathode electrode overlap region of a row-selected cathodeelectrode 11 and a column-selected anode electrode 33 (or acolumn-selected cathode electrode 11 and a row-selected anode electrode33). The electrons are drawn to the anode electrode 33, collide with thephosphor layer 31 constituting the anode panel AP, excite the phosphorlayer 31, and cause the phosphor layer 31 to emit light.

[0510] For forming the gate electrode, there may be employed othermethod in which a metal layer which is in the form of a band and has aplurality of opening portions formed therein is provided in advance, agate electrode supporting members composed of an insulating material inthe form of, for example, a band are formed on the supporting member 10in advance, and the metal layer is arranged above thecarbon-group-material layer or the selective-growth region such that themetal layer is in contact with the top surfaces of the gate electrodesupporting members. In this case, the selective-growth region and thecarbon-group-material layer may be formed before the arrangement of thegate electrode, or the selective-growth region and thecarbon-group-material layer may be formed after the arrangement of thegate electrode. Otherwise, the selective-growth region may be formedbefore the arrangement of the gate electrode, and thecarbon-group-material layer may be formed after the arrangement of thegate electrode. In these cases, the selective-growth region 20 may notbe formed right below the first opening portion 14A. In these case, thefield emission device or the display according to any one of the fourthto sixth aspects of the present invention can be obtained, and it comesto mean that the manufacturing method of a field emission device and themanufacturing method of a display according to any one of the seventh toninth aspects of the present invention are carried out.

[0511] The field emission device of the present invention may have aconstitution in which a second insulating layer 17 is further formed inthe gate electrode 13 and the insulating layer 12, and a focus electrode18 is formed on the second insulating layer 17. FIG. 19 shows aschematic partial end view of the thus-constituted field emissiondevice. The second insulating layer 17 has a third opening portion 19communicating with the first opening portion 14A. The focus electrode 18may be formed as follows. For example, in [Step-810] in Example 8, thegate electrode 13 in the form of a stripe is formed on the insulatinglayer 12, then, the second insulating layer 17 is formed, then, apatterned focus electrode 18 is formed on the second insulating layer17, the third opening portion 19 is formed in the focus electrode 18 andthe second insulating layer 17, and further, the first opening portion14A is formed in the gate electrode 13.

[0512] Not only the focus electrode is formed by the above method, butalso the focus electrode can be formed by forming an insulating filmmade, for example, of SiO₂ on each surface of a metal sheet made, forexample, of 42% Ni—Fe alloy having a thickness of several tensmicrometers, and then forming the opening portions in regionscorresponding to pixels by punching or etching. And, the cathode panel,the metal sheet and the anode panel are stacked, a frame is arranged incircumferential portions of the two panels, and a heat treatment iscarried out to bond the insulating film formed on one surface of themetal sheet and the insulating layer 12 and to bond the insulating filmformed on the other surface of the metal sheet and the anode panel,whereby these members are integrated, followed by evacuating andsealing. Whereby, the display can be also completed.

[0513] The gate electrode can be formed so as to have a form in whichthe effective field is covered with one sheet of an electricallyconductive material (having a first opening portion). In this case, apositive voltage is applied to the gate electrode. And, a switchingelement constituted, for example, of TFT is provided between the cathodeelectrode constituting a pixel and the cathode-electrode controlcircuit, and the voltage application state to the cathode electrodeconstituting the pixel is controlled by the operation of the aboveswitching element, to control the light emission state of the pixel.

[0514] Alternatively, the cathode electrode can be formed so as to havea form in which the effective filed is covered with one sheet of anelectrically conductive material. In this case, a voltage is applied tothe cathode electrode. And, a switching element constituted, forexample, of TFT is provided between the gate electrode constituting apixel and the gate-electrode control circuit, and the voltageapplication state to the gate electrode constituting the pixel iscontrolled by the operation of the switching element, to control thelight emission state of the pixel.

[0515] The anode electrode may be an anode electrode having a form inwhich the effective field is covered with one sheet-shaped electricallyconductive material or may be an anode electrode having a form in whichanode electrode units each of which corresponds to one or a plurality ofelectron emitting portions or one or a plurality of pixels are gathered.When the anode electrode has the former constitution, the anodeelectrode can be connected to the anode-electrode control circuit. Whenthe anode electrode has the latter constitution, for example, each anodeelectrode unit can be connected to the anode-electrode control circuit.

[0516] The electron emitting apparatus of the present invention can beapplied to a device generally called a surface-conduction-type electronemitting apparatus. The surface-conduction-type electron emittingapparatus comprises a supporting member made, for example, of glass andpairs of electrodes formed on the supporting member. The electrode iscomposed of an electrically conductive material such as tin oxide(SnO₂), gold (Au), indium oxide (In₂O₃)/tin oxide (SnO₂), carbon,palladium oxide (Pod), etc. The pair of the electrodes has a very smallarea and is arranged at a predetermined interval (gap). The pairs of theelectrodes are formed in the form of a matrix. And, thesurface-conduction-type electron emitting apparatus has a constitutionin which a wiring in the row direction is connected to one of each pairof the electrodes and a wiring in the column direction is connected tothe other of each pair of the electrodes. In the surface-conduction-typeelectron emitting apparatus, a selective-growth region is formed on thesurface of each pair of the electrodes (corresponding to theelectrically conductive layer), and the electron emitting portioncomprising the carbon-group-material layer is formed on theselective-growth region. When a voltage is applied to a pair of theelectrodes, an electric field is exerted on the carbon-group-materiallayers opposed to each other through the gap, and electrons are emittedfrom the carbon-group-material layer. Such electrons are attractedtoward the anode panel to collide with the phosphor layer on the anodepanel, so that the phosphor layer is excited to emit light and gives adesired image.

[0517] In the present invention, the electron emitting portion or thecarbon-group-material layer exhibits a kind of water repellency. As aresult, it is made possible to inhibit the adherence and adsorption of agas or gaseous substance released from various members constituting thecathode electrode and the display, particularly water, to/on theelectron emitting portion (specifically, the carbon-group-materiallayer). Therefore, the deterioration of properties of the electronemitting portion can be reliably prevented.

[0518] Further, since the electron emitting portion comprises thecarbon-group-material layer, there can be obtained a cold cathode fieldemission device or electron emitting apparatus having a low thresholdvoltage and high electron emission efficiency, and there can be alsoobtained a cold cathode field emission display that performs with a lowpower consumption and accomplishes high-quality images. Further, evenwhen the number of cold cathode field emission devices to be formed isincreased to a great extent due to an increase in the area of theeffective field, the electron emitting portions of the cold cathodefield emission devices can be highly accurately formed, so that theelectron emission efficiency of the electron emitting portions can bemade uniform over the entire area of the effective field, and there canbe manufactured a cold cathode field emission display that has almost nonon-uniformity in luminescence efficiency and accomplishes high-qualityimages. Further, since the carbon-group-material layer can be formed ata relatively low temperature, a glass substrate can be used as asupporting member, and the production cost can be decreased.

[0519] In the present invention, further, when the selective-growthregion is formed, the electron emitting portion comprising thecarbon-group-material layer can be formed in a predetermined portion ofthe electrically conductive layer or the cathode electrode, and that itis no longer necessary to pattern the carbon-group-material layer foradjusting the carbon-group-material layer to a predetermined form.Further, when the carbon nano-tube structures are employed to constitutethe electron emitting portion, the electron emitting portion can beeasily formed.

1. An electron emitting apparatus constituted of an electron emittingportion formed on an electrically conductive layer, the electronemitting portion comprising a carbon-group-material layer, and thecarbon-group-material layer being a layer formed from a hydrocarbon gasand a fluorine-containing hydrocarbon gas.
 2. The electron emittingapparatus according to claim 1, in which the electrically conductivelayer is constituted from copper, silver or gold.
 3. The electronemitting apparatus according to claim 1, in which a selective-growthregion is formed between the electrically conductive layer and thecarbon-group-material layer.
 4. An electron emitting apparatusconstituted of an electron emitting portion formed on an electricallyconductive layer, the electron emitting portion comprising acarbon-group-material layer and a fluoride-carbide-containing thin filmformed on the surface of the carbon-group-material layer, and thefluoride-carbide-containing thin film being a film formed from afluorine-containing hydrocarbon gas.
 5. The electron emitting apparatusaccording to claim 4, in which the carbon-group-material layer is alayer formed from a hydrocarbon gas.
 6. The electron emitting apparatusaccording to claim 5, in which the electrically conductive layer isconstituted from copper, silver or gold.
 7. The electron emittingapparatus according to claim 5, in which a selective-growth region isformed between the electrically conductive layer and thecarbon-group-material layer.
 8. The electron emitting apparatusaccording to claim 4, in which the carbon-group-material layer is formedof carbon-nano-tube structures.
 9. An electron emitting apparatusconstituted of an electron emitting portion formed on an electricallyconductive layer, the electron emitting portion comprising acarbon-group-material layer, and the carbon-group-material layer havinga surface terminated with fluorine atoms.
 10. The electron emittingapparatus according to claim 9, in which the termination of the surfaceof the carbon-group-material layer with fluorine atoms is carried outwith a fluorine-containing hydrocarbon gas.
 11. The electron emittingapparatus according to claim 9, in which the carbon-group-material layeris a layer formed from a hydrocarbon gas.
 12. The electron emittingapparatus according to claim 11, in which the electrically conductivelayer is constituted from copper, silver or gold.
 13. The electronemitting apparatus according to claim 11, in which a selective-growthregion is formed between the electrically conductive layer and thecarbon-group-material layer.
 14. The electron emitting apparatusaccording to claim 9, in which the carbon-group-material layer is formedof carbon-nano-tube structures.
 15. A cold cathode field emission devicecomprising; (a) a cathode electrode formed on a supporting member, and(b) an electron emitting portion formed on the cathode electrode, inwhich the electron emitting portion comprises a carbon-group-materiallayer, and the carbon-group-material layer is a layer formed from ahydrocarbon gas and a fluorine-containing hydrocarbon gas.
 16. The coldcathode field emission device according to claim 15, in which aselective-growth region is formed between the cathode electrode and thecarbon-group-material layer.
 17. A cold cathode field emission devicecomprising; (a) a cathode electrode formed on a supporting member, and(b) an electron emitting portion formed on the cathode electrode, inwhich the electron emitting portion comprises a carbon-group-materiallayer and a fluoride-carbide-containing thin film formed on the surfaceof the carbon-group-material layer, and the fluoride-carbide-containingthin film is a film formed from a fluorine-containing hydrocarbon gas.18. The cold cathode field emission device according to claim 17, inwhich the carbon-group-material layer is a layer formed from ahydrocarbon gas.
 19. The cold cathode field emission device according toclaim 18, in which a selective-growth region is formed between thecathode electrode and the carbon-group-material layer.
 20. The coldcathode field emission device according to claim 17, in which thecarbon-group-material layer is formed of carbon-nano-tube structures.21. A cold cathode field emission device comprising; (a) a cathodeelectrode formed on a supporting member, and (b) an electron emittingportion formed on the cathode electrode, in which the electron emittingportion comprises a carbon-group-material layer, and thecarbon-group-material layer has a surface terminated with fluorineatoms.
 22. The cold cathode field emission device according to claim 21,in which the termination of the surface of the carbon-group-materiallayer with fluorine atoms is carried out with a fluorine-containinghydrocarbon gas.
 23. The cold cathode field emission device according toclaim 21, in which the carbon-group-material layer is a layer formedfrom a hydrocarbon gas.
 24. The cold cathode field emission deviceaccording to claim 23, in which a selective-growth region is formedbetween the cathode electrode and the carbon-group-material layer. 25.The cold cathode field emission device according to claim 21, in whichthe carbon-group-material layer is formed of carbon-nano-tubestructures.
 26. A cold cathode field emission device comprising; (a) acathode electrode formed on a supporting member, (b) a gate electrodewhich is formed above the cathode electrode and has an opening portion,and (c) an electron emitting portion formed in a portion of the cathodeelectrode which portion is positioned in a bottom portion of the openingportion, in which the electron emitting portion comprises acarbon-group-material layer, and the carbon-group-material layer is alayer formed from a hydrocarbon gas and a fluorine-containinghydrocarbon gas.
 27. The cold cathode field emission device according toclaim 26, in which the cathode electrode is constituted from copper,silver or gold.
 28. The cold cathode field emission device according toclaim 26, in which a selective-growth region is formed at least betweenthe cathode electrode and the carbon-group-material layer.
 29. The coldcathode field emission device according to claim 26, in which aninsulating layer is formed on the supporting member and the cathodeelectrode, and a second opening portion communicating with the openingportion made through the gate electrode is made through the insulatinglayer.
 30. A cold cathode field emission device comprising; (a) acathode electrode formed on a supporting member, (b) a gate electrodewhich is formed above the cathode electrode and has an opening portion,and (c) an electron emitting portion formed in a portion of the cathodeelectrode which portion is positioned in a bottom portion of the openingportion, in which the electron emitting portion comprises acarbon-group-material layer and a fluoride-carbide-containing thin filmformed on the surface of the carbon-group-material layer, and thefluoride-carbide-containing thin film is a film formed from afluorine-containing hydrocarbon gas.
 31. The cold cathode field emissiondevice according to claim 30, in which the carbon-group-material layeris a layer formed from a hydrocarbon gas.
 32. The cold cathode fieldemission device according to claim 31, in which the cathode electrode isconstituted from copper, silver or gold.
 33. The cold cathode fieldemission device according to claim 31, in which a selective-growthregion is formed at least between the cathode electrode and thecarbon-group-material layer.
 34. The cold cathode field emission deviceaccording to claim 30, in which an insulating layer is formed on thesupporting member and the cathode electrode, and a second openingportion communicating with the opening portion made through the gateelectrode is made through the insulating layer.
 35. The cold cathodefield emission device according to claim 30, in which thecarbon-group-material layer is formed of carbon-nano-tube structures.36. A cold cathode field emission device comprising; (a) a cathodeelectrode formed on a supporting member, (b) a gate electrode which isformed above the cathode electrode and has an opening portion, and (c)an electron emitting portion formed in a portion of the cathodeelectrode which portion is positioned in a bottom portion of the openingportion, in which the electron emitting portion comprises acarbon-group-material layer, and the carbon-group-material layer has asurface terminated with fluorine atoms.
 37. The cold cathode fieldemission device according to claim 36, in which the termination of thesurface of the carbon-group-material layer with fluorine atoms iscarried out with a fluorine-containing hydrocarbon gas.
 38. The coldcathode field emission device according to claim 36, in which thecarbon-group-material layer is a layer formed from a hydrocarbon gas.39. The cold cathode field emission device according to claim 38, inwhich the cathode electrode is constituted from copper, silver or gold.40. The cold cathode field emission device according to claim 38, inwhich a selective-growth region is formed at least between the cathodeelectrode and the carbon-group-material layer.
 41. The cold cathodefield emission device according to claim 36, in which an insulatinglayer is formed on the supporting member and the cathode electrode, anda second opening portion communicating with the opening portion madethrough the gate electrode is made through the insulating layer.
 42. Thecold cathode field emission device according to claim 36, in which thecarbon-group-material layer is formed of carbon-nano-tube structures.43. A cold cathode field emission display having a plurality of pixels,each pixel being constituted of a cold cathode field emission device, ananode electrode and a phosphor layer, said anode electrode and saidphosphor layer being formed on a substrate so as to face the coldcathode field emission device, and the cold cathode field emissiondevice comprising; (a) a cathode electrode formed a supporting member,and (b) an electron emitting portion formed on the cathode electrode, inwhich the electron emitting portion comprises a carbon-group-materiallayer, and the carbon-group-material layer is a layer formed from ahydrocarbon gas and a fluorine-containing hydrocarbon gas.
 44. The coldcathode field emission display according to claim 43, in which aselective-growth region is formed between the cathode electrode and thecarbon-group-material layer.
 45. A cold cathode field emission displayhaving a plurality of pixels, each pixel being constituted of a coldcathode field emission device, an anode electrode and a phosphor layer,said anode electrode and said phosphor layer being formed on a substrateso as to face the cold cathode field emission device, and the coldcathode field emission device comprising; (a) a cathode electrode formeda supporting member, and (b) an electron emitting portion formed on thecathode electrode, in which the electron emitting portion comprises acarbon-group-material layer and a fluoride-carbide-containing thin filmformed on the surface of the carbon-group-material layer, and thefluoride-carbide-containing thin film is a film formed from afluorine-containing hydrocarbon gas.
 46. The cold cathode field emissiondisplay according to claim 45, in which the carbon-group-material layeris a layer formed from a hydrocarbon gas.
 47. The cold cathode fieldemission display according to claim 46, in which a selective-growthregion is formed between the cathode electrode and thecarbon-group-material layer.
 48. The cold cathode field emission displayaccording to claim 45, in which the carbon-group-material layer isformed of carbon-nano-tube structures.
 49. A cold cathode field emissiondisplay having a plurality of pixels, each pixel being constituted of acold cathode field emission device, an anode electrode and a phosphorlayer, said anode electrode and said phosphor layer being formed on asubstrate so as to face the cold cathode field emission device, and thecold cathode field emission device comprising; (a) a cathode electrodeformed a supporting member, and (b) an electron emitting portion formedon the cathode electrode, in which the electron emitting portioncomprises a carbon-group-material layer, and the carbon-group-materiallayer has a surface terminated with fluorine atoms.
 50. The cold cathodefield emission display according to claim 49, in which the terminationof the surface of the carbon-group-material layer with fluorine atoms iscarried out with a fluorine-containing hydrocarbon gas.
 51. The coldcathode field emission display according to claim 49, in which thecarbon-group-material layer is a layer formed from a hydrocarbon gas.52. The cold cathode field emission display according to claim 51, inwhich a selective-growth region is formed between the cathode electrodeand the carbon-group-material layer.
 53. The cold cathode field emissiondisplay according to claim 49, in which the carbon-group-material layeris formed of carbon-nano-tube structures.
 54. A cold cathode fieldemission display having a plurality of pixels, each pixel beingconstituted of a cold cathode field emission device, an anode electrodeand a phosphor layer, said anode electrode and said phosphor layer beingformed on a substrate so as to face the cold cathode field emissiondevice, and the cold cathode field emission device comprising; (a) acathode electrode formed on a supporting member, (b) a gate electrodewhich is formed above the cathode electrode and has an opening portion,and (c) an electron emitting portion formed on a portion of the cathodeelectrode which portion is positioned in a bottom portion of the openingportion, in which the electron emitting portion comprises acarbon-group-material layer, and the carbon-group-material layer is alayer formed from a hydrocarbon gas and a fluorine-containinghydrocarbon gas.
 55. The cold cathode field emission display accordingto claim 54, in which the cathode electrode is constituted from copper,silver or gold.
 56. The cold cathode field emission display according toclaim 54, in which a selective-growth region is formed at least betweenthe cathode electrode and the carbon-group-material layer.
 57. The coldcathode field emission display according to claim 54, in which aninsulating layer is formed on the supporting member and the cathodeelectrode, and a second opening portion communicating with the openingportion made through the gate electrode is made through the insulatinglayer.
 58. A cold cathode field emission display having a plurality ofpixels, each pixel being constituted of a cold cathode field emissiondevice, an anode electrode and a phosphor layer, said anode electrodeand said phosphor layer being formed on a substrate so as to face thecold cathode field emission device, and the cold cathode field emissiondevice comprising; (a) a cathode electrode formed on a supportingmember, (b) a gate electrode which is formed above the cathode electrodeand has an opening portion, and (c) an electron emitting portion formedon a portion of the cathode electrode which portion is positioned in abottom portion of the opening portion, in which the electron emittingportion comprises a carbon-group-material layer and afluoride-carbide-containing thin film formed on the surface of thecarbon-group-material layer, and the fluoride-carbide-containing thinfilm is a film formed from a fluorine-containing hydrocarbon gas. 59.The cold cathode field emission display according to claim 58, in whichthe carbon-group-material layer is a layer formed from a hydrocarbongas.
 60. The cold cathode field emission display according to claim 59,in which the cathode electrode is constituted from copper, silver orgold.
 61. The cold cathode field emission display according to claim 59,in which a selective-growth region is formed at least between thecathode electrode and the carbon-group-material layer.
 62. The coldcathode field emission display according to claim 58, in which aninsulating layer is formed on the supporting member and the cathodeelectrode, and a second opening portion communicating with the openingportion made through the gate electrode is made through the insulatinglayer.
 63. The cold cathode field emission display according to claim58, in which the carbon-group-material layer is formed ofcarbon-nano-tube structures.
 64. A cold cathode field emission displayhaving a plurality of pixels, each pixel being constituted of a coldcathode field emission device, an anode electrode and a phosphor layer,said anode electrode and said phosphor layer being formed on a substrateso as to face the cold cathode field emission device, and the coldcathode field emission device comprising; (a) a cathode electrode formedon a supporting member, (b) a gate electrode which is formed above thecathode electrode and has an opening portion, and (c) an electronemitting portion formed on a portion of the cathode electrode whichportion is positioned in a bottom portion of the opening portion, inwhich the electron emitting portion comprises a carbon-group-materiallayer, and the carbon-group-material layer has a surface terminated withfluorine atoms.
 65. The cold cathode field emission display according toclaim 64, in which the termination of the surface of thecarbon-group-material layer with fluorine atoms is carried out with afluorine-containing hydrocarbon gas.
 66. The cold cathode field emissiondisplay according to claim 64, in which the carbon-group-material layeris a layer formed from a hydrocarbon gas.
 67. The cold cathode fieldemission display according to claim 66, in which the cathode electrodeis constituted from copper, silver or gold.
 68. The cold cathode fieldemission display according to claim 66, in which a selective-growthregion is formed at least between the cathode electrode and thecarbon-group-material layer.
 69. The cold cathode field emission displayaccording to claim 64, in which an insulating layer is formed on thesupporting member and the cathode electrode, and a second openingportion communicating with the opening portion made through the gateelectrode is made through the insulating layer.
 70. The cold cathodefield emission display according to claim 64, in which thecarbon-group-material layer is formed of carbon-nano-tube structures.71. A manufacturing method of an electron emitting apparatus comprisingthe step of forming an electron emitting portion comprising acarbon-group-material layer, on an electrically conductive layer, from ahydrocarbon gas and a fluorine-containing hydrocarbon gas.
 72. Themanufacturing method of an electron emitting apparatus according toclaim 71, in which further provided is the step of forming aselective-growth region on the electrically conductive layer before theformation of the carbon-group-material layer.
 73. A manufacturing methodof an electron emitting apparatus comprising the steps of; (A) forming acarbon-group-material layer on an electrically conductive layer, and (B)forming a fluoride-carbide-containing thin film on the surface of thecarbon-group-material layer from a fluorine-containing hydrocarbon gas,thereby to obtain an electron emitting portion comprising thecarbon-group-material layer and the fluoride-carbide-containing thinfilm formed on the surface of the carbon-group-material layer.
 74. Themanufacturing method of an electron emitting apparatus according toclaim 73, in which the carbon-group-material layer is formed on theelectrically conductive layer from a hydrocarbon gas in the step (A).75. The manufacturing method of an electron emitting apparatus accordingto claim 74, in which further provided is the step of forming aselective-growth region on the electrically conductive layer before theformation of the carbon-group-material layer.
 76. The manufacturingmethod of an electron emitting apparatus according to claim 73, in whicha dispersion of carbon-nano-tube structures in a binder material isapplied onto the electrically conductive layer and then the bindermaterial is fired or cured to form the carbon-group-material layer inthe step (A).
 77. The manufacturing method of an electron emittingapparatus according to claim 73, in which a metal compound solution inwhich carbon-nano-tube structures are dispersed is applied onto theelectrically conductive layer, and then the metal compound is fired, toform the carbon-group-material layer in the step (A).
 78. Amanufacturing method of an electron emitting apparatus comprising thesteps of; (A) forming a carbon-group-material layer on an electricallyconductive layer, and (B) terminating the surface of thecarbon-group-material layer with a fluorine-containing hydrocarbon gas,thereby to obtain an electron emitting portion comprising thecarbon-group-material layer whose surface is terminated with fluorineatoms.
 79. The manufacturing method of an electron emitting apparatusaccording to claim 78, in which the carbon-group-material layer isformed on the electrically conductive layer from a hydrocarbon gas inthe step (A).
 80. The manufacturing method of an electron emittingapparatus according to claim 79, in which further provided is the stepof forming a selective-growth region on the electrically conductivelayer before the formation of the carbon-group-material layer.
 81. Themanufacturing method of an electron emitting apparatus according toclaim 78, in which a dispersion of carbon-nano-tube structures in abinder material is applied onto the electrically conductive layer andthen the binder material is fired or cured to form thecarbon-group-material layer in the step (A).
 82. The manufacturingmethod of an electron emitting apparatus according to claim 78, in whicha metal compound solution in which carbon-nano-tube structures aredispersed is applied onto the electrically conductive layer, and thenthe metal compound is fired, to form the carbon-group-material layer inthe step (A).
 83. A manufacturing method of a cold cathode fieldemission device comprising the steps of; (A) forming a cathode electrodeon a supporting member, and (B) forming an electron emitting portion onthe cathode electrode, in which the electron emitting portion comprisesa carbon-group-material layer, and the step of forming the electronemitting portion comprises the step of forming the carbon-group-materiallayer from a hydrocarbon gas and a fluorine-containing hydrocarbon gas.84. The manufacturing method of a cold cathode field emission deviceaccording to claim 83, in which interposed between the step (A) and thestep (B) is the step of forming a selective-growth region on the cathodeelectrode, and the step (B) is carried out by forming the electronemitting portion on the selective-growth region in place of forming theelectron emitting portion on the cathode electrode.
 85. A manufacturingmethod of a cold cathode field emission device comprising the steps of;(A) forming a cathode electrode on a supporting member, (B) forming acarbon-group-material layer on the cathode electrode, and (C) forming afluoride-carbide-containing thin film on the surface of thecarbon-group-material layer from a fluorine-containing hydrocarbon gas,thereby to obtain an electron emitting portion comprising thecarbon-group-material layer and the fluoride-carbide-containing thinfilm formed on the surface of the carbon-group-material layer.
 86. Themanufacturing method of a cold cathode field emission device accordingto claim 85, in which the carbon-group-material layer is formed on thecathode electrode from a hydrocarbon gas in the step (B).
 87. Themanufacturing method of a cold cathode field emission device accordingto claim 86, in which interposed between the steps (A) and (B) is thestep of forming a selective-growth region on the cathode electrode, andin the (B), the electron emitting portion is formed on theselective-growth region in place of forming the electron emittingportion on the cathode electrode.
 88. The manufacturing method of a coldcathode field emission device according to claim 85, in which adispersion of carbon nano-tube structures in a binder material isapplied onto the cathode electrode and the binder material is fired orcured to form the carbon-group-material layer in the step of forming theelectron emitting portion.
 89. The manufacturing method of a coldcathode field emission device according to claim 85, in which a metalcompound solution in which carbon nano-tube structures are dispersed isapplied onto the cathode electrode and then the metal compound is fired,to form the carbon-group-material layer in the step of forming theelectron emitting portion.
 90. A manufacturing method of a cold cathodefield emission device comprising the steps of; (A) forming a cathodeelectrode on a supporting member, (B) forming a carbon-group-materiallayer on the cathode electrode, and (C) terminating the surface of thecarbon-group-material layer with a fluorine-containing hydrocarbon gas,thereby to obtain an electron emitting portion comprising thecarbon-group-material layer having the surface terminated with fluorineatoms.
 91. The manufacturing method of a cold cathode field emissiondevice according to claim 90, in which the carbon-group-material layeris formed on the cathode electrode from a hydrocarbon gas in the step(B).
 92. The manufacturing method of a cold cathode field emissiondevice according to claim 91, in which interposed between the steps (A)and (B) is the step of forming a selective-growth region on the cathodeelectrode, and in the (B), the electron emitting portion is formed onthe selective-growth region in place of forming the electron emittingportion on the cathode electrode.
 93. The manufacturing method of a coldcathode field emission device according to claim 90, in which adispersion of carbon nano-tube structures in a binder material isapplied onto the cathode electrode and the binder material is fired orcured to form the carbon-group-material layer in the step of forming theelectron emitting portion.
 94. The manufacturing method of a coldcathode field emission device according to claim 90, in which a metalcompound solution in which carbon nano-tube structures are dispersed isapplied onto the cathode electrode and then the metal compound is fired,to form the carbon-group-material layer in the step of forming theelectron emitting portion.
 95. A manufacturing method of a cold cathodefield emission device comprising the steps of; (A) forming a cathodeelectrode on a supporting member, (B) forming an insulating layer on thesupporting member and the cathode electrode, (C) forming a gateelectrode having an opening portion on the insulating layer, (D) forminga second opening portion through the insulating layer, said secondopening portion communicating with the opening portion formed throughthe gate electrode, thereby to expose the cathode electrode in a bottomportion of the second opening portion, and (E) forming an electronemitting portion on the cathode electrode exposed in the bottom portionof the second opening portion, in which the electron emitting portioncomprises a carbon-group-material layer, and the step of forming theelectron emitting portion comprises the step of forming thecarbon-group-material layer from a hydrocarbon gas and afluorine-containing hydrocarbon gas.
 96. The manufacturing method of acold cathode field emission device according to claim 95, in whichinterposed between the step (A) and the step (B) is the step of forminga selective-growth region on the cathode electrode, an insulating layeris formed on the supporting member, the selective-growth region and thecathode electrode in the step (B), a second opening portion is formedthrough the insulating layer in the step (D), said second openingportion communicating with the opening portion formed through the gateelectrode, thereby to expose the selective-growth region in the bottomportion of the second opening portion, and the electron emitting portionis formed on the selective-growth region exposed in the bottom portionof the second opening portion in the step (E).
 97. The manufacturingmethod of a cold cathode field emission device according to claim 95, inwhich interposed between the step (D) and the step (E) is the step offorming a selective-growth region on the cathode electrode exposed inthe bottom portion of the second opening portion, and the electronemitting portion is formed on the selective-growth region in the step(E) in place of forming the electron emitting portion on the cathodeelectrode exposed in the bottom portion of the second opening portion.98. A manufacturing method of a cold cathode field emission devicecomprising the steps of; (A) forming a cathode electrode on a supportingmember, (B) forming an insulating layer on the supporting member and thecathode electrode, (C) forming a gate electrode having an openingportion on the insulating layer, (D) forming a second opening portionthrough the insulating layer, said second opening portion communicatingwith the opening portion formed through the gate electrode, thereby toexpose the cathode electrode in a bottom portion of the second openingportion, and (E) forming an electron emitting portion on the cathodeelectrode exposed in the bottom portion of the second opening portion,in which the electron emitting portion comprises a carbon-group-materiallayer and a fluoride-carbide-containing thin film formed on the surfaceof the carbon-group-material layer, and the step of forming the electronemitting portion comprises the step of forming thefluoride-carbide-containing thin film on the surface of the formedcarbon-group-material layer from a fluorine-containing hydrocarbon gas.99. The manufacturing method of a cold cathode field emission deviceaccording to claim 98, in which the carbon-group-material layer isformed from a hydrocarbon gas in the step of forming the electronemitting portion.
 100. The manufacturing method of a cold cathode fieldemission device according to claim 99, in which interposed between thestep (A) and the step (B) is the step of forming a selective-growthregion on the cathode electrode, an insulating layer is formed on thesupporting member, the selective-growth region and the cathode electrodein the step (B), a second opening portion is formed through theinsulating layer in the step (D), said second opening portioncommunicating with the opening portion formed through the gateelectrode, thereby to expose the selective-growth region in the bottomportion of the second opening portion, and the electron emitting portionis formed on the selective-growth region exposed in the bottom portionof the second opening portion in the step (E).
 101. The manufacturingmethod of a cold cathode field emission device according to claim 99, inwhich interposed between the step (D) and the step (E) is the step offorming a selective-growth region on the cathode electrode exposed inthe bottom portion of the second opening portion, and the electronemitting portion is formed on the selective-growth region in the step(E) in place of forming the electron emitting portion on the cathodeelectrode exposed in the bottom portion of the second opening portion.102. The manufacturing method of a cold cathode field emission deviceaccording to claim 98, in which a dispersion of carbon nano-tubestructures in a binder material is applied onto the cathode electrodeand the binder material is fired or cured to form thecarbon-group-material layer in the step of forming the electron emittingportion.
 103. The manufacturing method of a cold cathode field emissiondevice according to claim 98, in which a metal compound solution inwhich carbon nano-tube structures are dispersed is applied onto thecathode electrode and then the metal compound is fired, to form thecarbon-group-material layer in the step of forming the electron emittingportion.
 104. A manufacturing method of a cold cathode field emissiondevice comprising the steps of; (A) forming a cathode electrode on asupporting member, (B) forming an insulating layer on the supportingmember and the cathode electrode, (C) forming a gate electrode having anopening portion on the insulating layer, (D) forming a second openingportion through the insulating layer, said second opening portioncommunicating with the opening portion formed through the gateelectrode, thereby to expose the cathode electrode in a bottom portionof the second opening portion, and (E) forming an electron emittingportion on the cathode electrode exposed in the bottom portion of thesecond opening portion, in which the electron emitting portion comprisesa carbon-group-material layer, and the step of forming the electronemitting portion comprises the step of terminating the surface of theformed carbon-group-material layer with a fluorine-containinghydrocarbon gas.
 105. The manufacturing method of a cold cathode fieldemission device according to claim 104, in which thecarbon-group-material layer is formed from a hydrocarbon gas in the stepof forming the electron emitting portion.
 106. The manufacturing methodof a cold cathode field emission device according to claim 105, in whichinterposed between the step (A) and the step (B) is the step of forminga selective-growth region on the cathode electrode, an insulating layeris formed on the supporting member, the selective-growth region and thecathode electrode in the step (B), a second opening portion is formedthrough the insulating layer in the step (D), said second openingportion communicating with the opening portion formed through the gateelectrode, thereby to expose the selective-growth region in the bottomportion of the second opening portion, and the electron emitting portionis formed on the selective-growth region exposed in the bottom portionof the second opening portion in the step (E).
 107. The manufacturingmethod of a cold cathode field emission device according to claim 105,in which interposed between the step (D) and the step (E) is the step offorming a selective-growth region on the cathode electrode exposed inthe bottom portion of the second opening portion, and the electronemitting portion is formed on the selective-growth region in the step(E) in place of forming the electron emitting portion on the cathodeelectrode exposed in the bottom portion of the second opening portion.108. The manufacturing method of a cold cathode field emission deviceaccording to claim 104, in which a dispersion of carbon nano-tubestructures in a binder material is applied onto the cathode electrodeand the binder material is fired or cured to form thecarbon-group-material layer in the step of forming the electron emittingportion.
 109. The manufacturing method of a cold cathode field emissiondevice according to claim 104, in which a metal compound solution inwhich carbon nano-tube structures are dispersed is applied onto thecathode electrode and then the metal compound is fired, to form thecarbon-group-material layer in the step of forming the electron emittingportion.
 110. A manufacturing method of a cold cathode field emissiondevice comprising the steps of; (A) forming a cathode electrode on asupporting member, (B) forming an electron emitting portion on thecathode electrode, and (C) forming a gate electrode having an openingportion above the electron emitting portion, in which the electronemitting portion comprises a carbon-group-material layer, and the stepof forming the electron emitting portion comprises the step of formingthe carbon-group-material layer from a hydrocarbon gas and afluorine-containing hydrocarbon gas.
 111. The manufacturing method of acold cathode field emission device according to claim 110, in which thestep (B) is followed by forming an insulating layer on the entiresurface, and the step (C) is followed by forming a second openingportion through the insulating layer, said second opening portioncommunicating with the opening portion formed through the gateelectrode, thereby to expose the carbon-group-material layer in a bottomportion of the second opening portion.
 112. The manufacturing method ofa cold cathode field emission device according to claim 110, in whichinterposed between the step (A) and the step (B) is the step of forminga selective-growth region on the cathode electrode, and the electronemitting portion is formed on the selective-growth region in the step(B) in place of forming the electron emitting portion on the cathodeelectrode.
 113. A manufacturing method of a cold cathode field emissiondevice comprising the steps of; (A) forming a cathode electrode on asupporting member, (B) forming an electron emitting portion on thecathode electrode, and (C) forming a gate electrode having an openingportion above the electron emitting portion, in which the electronemitting portion comprises a carbon-group-material layer and afluoride-carbide-containing thin film formed on the surface of thecarbon-group-material layer, and the step of forming the electronemitting portion comprises the step of forming thefluoride-carbide-containing thin film on the surface of the formedcarbon-group-material layer from a fluorine-containing hydrocarbon gas.114. The manufacturing method of a cold cathode field emission deviceaccording to claim 113, in which the step (B) is followed by forming aninsulating layer on the entire surface, and the step (C) is followed byforming a second opening portion through the insulating layer, saidsecond opening portion communicating with the opening portion formedthrough the gate electrode, thereby to expose the carbon-group-materiallayer in a bottom portion of the second opening portion.
 115. Themanufacturing method of a cold cathode field emission device accordingto claim 113, in which the carbon-group-material layer is formed from ahydrocarbon gas in the step of forming the electron emitting portion.116. The manufacturing method of a cold cathode field emission deviceaccording to claim 115, in which interposed between the step (A) and thestep (B) is the step of forming a selective-growth region on the cathodeelectrode, and the electron emitting portion is formed on theselective-growth region in the step (B) in place of forming the electronemitting portion on the cathode electrode.
 117. The manufacturing methodof a cold cathode field emission device according to claim 113, in whicha dispersion of carbon nano-tube structures in a binder material isapplied onto the cathode electrode and the binder material is fired orcured to form the carbon-group-material layer in the step of forming theelectron emitting portion.
 118. The manufacturing method of a coldcathode field emission device according to claim 113, in which a metalcompound solution in which carbon nano-tube structures are dispersed isapplied onto the cathode electrode and then the metal compound is fired,to form the carbon-group-material layer in the step of forming theelectron emitting portion.
 119. A manufacturing method of a cold cathodefield emission device comprising the steps of; (A) forming a cathodeelectrode on a supporting member, (B) forming an electron emittingportion on the cathode electrode, and (C) forming a gate electrodehaving an opening portion above the electron emitting portion, in whichthe electron emitting portion comprises a carbon-group-material layer,and the step of forming the electron emitting portion comprises the stepof terminating the surface of the formed carbon-group-material layerwith a fluorine-containing hydrocarbon gas.
 120. The manufacturingmethod of a cold cathode field emission device according to claim 119,in which the step (B) is followed by forming an insulating layer on theentire surface, and the step (C) is followed by forming a second openingportion through the insulating layer, said second opening portioncommunicating with the opening portion formed through the gateelectrode, thereby to expose the carbon-group-material layer in a bottomportion of the second opening portion.
 121. The manufacturing method ofa cold cathode field emission device according to claim 119, in whichthe carbon-group-material layer is formed from a hydrocarbon gas in thestep of forming the electron emitting portion.
 122. The manufacturingmethod of a cold cathode field emission device according to claim 121,in which interposed between the step (A) and the step (B) is the step offorming a selective-growth region on the cathode electrode, and theelectron emitting portion is formed on the selective-growth region inthe step (B) in place of forming the electron emitting portion on thecathode electrode.
 123. The manufacturing method of a cold cathode fieldemission device according to claim 119, in which a dispersion of carbonnano-tube structures in a binder material is applied onto the cathodeelectrode and the binder material is fired or cured to form thecarbon-group-material layer in the step of forming the electron emittingportion.
 124. The manufacturing method of a cold cathode field emissiondevice according to claim 119, in which a metal compound solution inwhich carbon nano-tube structures are dispersed is applied onto thecathode electrode and then the metal compound is fired, to form thecarbon-group-material layer in the step of forming the electron emittingportion.
 125. A manufacturing method of a cold cathode field emissiondisplay, in which a substrate having an anode electrode and a phosphorlayer formed thereon and a supporting member having a cold cathode fieldemission device formed thereon are arranged such that the phosphor layerand the cold cathode field emission device face each other, and thesubstrate and the supporting member are bonded to each other in theircircumferential portions, the method including the steps of; (A) forminga cathode electrode on the supporting member, and (B) forming anelectron emitting portion on the cathode electrode, thereby to form thecold cathode field emission device, in which the electron emittingportion comprises a carbon-group-material layer, and the step of formingthe electron emitting portion comprises the step of forming thecarbon-group-material layer from a hydrocarbon gas and afluorine-containing hydrocarbon gas.
 126. The manufacturing method of acold cathode field emission display according to claim 125, in whichinterposed between the step (A) and the step (B) is the step of forminga selective-growth region on the cathode electrode, and the step (B) iscarried out by forming the electron emitting portion on theselective-growth region in place of forming the electron emittingportion on the cathode electrode.
 127. A manufacturing method of a coldcathode field emission display, in which a substrate having an anodeelectrode and a phosphor layer formed thereon and a supporting memberhaving a cold cathode field emission device formed thereon are arrangedsuch that the phosphor layer and the cold cathode field emission deviceface each other, and the substrate and the supporting member are bondedto each other in their circumferential portions, the method includingthe steps of; (A) forming a cathode electrode on the supporting member,(B) forming a carbon-group-material layer on the cathode electrode, and(C) forming a fluoride-carbide-containing thin film on the surface ofthe carbon-group-material layer from a fluorine-containing hydrocarbongas, thereby to obtain an electron emitting portion comprising thecarbon-group-material layer and the fluoride-carbide-containing thinfilm formed on the surface of the carbon-group-material layer, wherebythe cold cathode field emission device is formed.
 128. The manufacturingmethod of a cold cathode field emission display according to claim 127,in which the carbon-group-material layer is formed on the cathodeelectrode from a hydrocarbon gas in the step (B).
 129. The manufacturingmethod of a cold cathode field emission display according to claim 128,in which interposed between the steps (A) and (B) is the step of forminga selective-growth region on the cathode electrode, and in the (B), theelectron emitting portion is formed on the selective-growth region inplace of forming the electron emitting portion on the cathode electrode.130. The manufacturing method of a cold cathode field emission displayaccording to claim 127, in which a dispersion of carbon nano-tubestructures in a binder material is applied onto the cathode electrodeand the binder material is fired or cured to form thecarbon-group-material layer in the step of forming the electron emittingportion.
 131. The manufacturing method of a cold cathode field emissiondisplay according to claim 127, in which a metal compound solution inwhich carbon nano-tube structures are dispersed is applied onto thecathode electrode and then the metal compound is fired, to form thecarbon-group-material layer in the step of forming the electron emittingportion.
 132. A manufacturing method of a cold cathode field emissiondisplay, in which a substrate having an anode electrode and a phosphorlayer formed thereon and a supporting member having a cold cathode fieldemission device formed thereon are arranged such that the phosphor layerand the cold cathode field emission device face each other, and thesubstrate and the supporting member are bonded to each other in theircircumferential portions, the method including the steps of; (A) forminga cathode electrode on the supporting member, (B) forming acarbon-group-material layer on the cathode electrode, and (C)terminating the surface of the carbon-group-material layer with afluorine-containing hydrocarbon gas, thereby to obtain an electronemitting portion comprising the carbon-group-material layer having thesurface terminated with fluorine atoms, whereby the cold cathode fieldemission device is formed.
 133. The manufacturing method of a coldcathode field emission display according to claim 132, in which thecarbon-group-material layer is formed on the cathode electrode from ahydrocarbon gas in the step (B).
 134. The manufacturing method of a coldcathode field emission display according to claim 133, in whichinterposed between the steps (A) and (B) is the step of forming aselective-growth region on the cathode electrode, and in the (B), theelectron emitting portion is formed on the selective-growth region inplace of forming the electron emitting portion on the cathode electrode.135. The manufacturing method of a cold cathode field emission displayaccording to claim 132, in which a dispersion of carbon nano-tubestructures in a binder material is applied onto the cathode electrodeand the binder material is fired or cured to form thecarbon-group-material layer in the step of forming the electron emittingportion.
 136. The manufacturing method of a cold cathode field emissiondisplay according to claim 132, in which a metal compound solution inwhich carbon nano-tube structures are dispersed is applied onto thecathode electrode and then the metal compound is fired, to form thecarbon-group-material layer in the step of forming the electron emittingportion.
 137. A manufacturing method of a cold cathode field emissiondisplay, in which a substrate having an anode electrode and a phosphorlayer formed thereon and a supporting member having a cold cathode fieldemission device formed thereon are arranged such that the phosphor layerand the cold cathode field emission device face each other, and thesubstrate and the supporting member are bonded to each other in theircircumferential portions, the method including the steps of; (A) forminga cathode electrode on the supporting member, (B) forming an insulatinglayer on the supporting member and the cathode electrode, (C) forming agate electrode having an opening portion on the insulating layer, (D)forming a second opening portion through the insulating layer, saidsecond opening portion communicating with the opening portion formedthrough the gate electrode, thereby to expose the cathode electrode in abottom portion of the second opening portion, and (E) forming anelectron emitting portion on the cathode electrode exposed in the bottomportion of the second opening portion, whereby the cold cathode fieldemission device is formed, in which the electron emitting portioncomprises a carbon-group-material layer, and the step of forming theelectron emitting portion comprises the step of forming thecarbon-group-material layer from a hydrocarbon gas and afluorine-containing hydrocarbon gas.
 138. The manufacturing method of acold cathode field emission display according to claim 137, in whichinterposed between the step (A) and the step (B) is the step of forminga selective-growth region on the cathode electrode, an insulating layeris formed on the supporting member, the selective-growth region and thecathode electrode in the step (B), a second opening portion is formedthrough the insulating layer in the step (D), said second openingportion communicating with the opening portion formed through the gateelectrode, thereby to expose the selective-growth region in the bottomportion of the second opening portion, and the electron emitting portionis formed on the selective-growth region exposed in the bottom portionof the second opening portion in the step (E).
 139. The manufacturingmethod of a cold cathode field emission display according to claim 137,in which interposed between the step (D) and the step (E) is the step offorming a selective-growth region on the cathode electrode exposed inthe bottom portion of the second opening portion, and the electronemitting portion is formed on the selective-growth region in the step(E) in place of forming the electron emitting portion on the cathodeelectrode exposed in the bottom portion of the second opening portion.140. A manufacturing method of a cold cathode field emission display, inwhich a substrate having an anode electrode and a phosphor layer formedthereon and a supporting member having a cold cathode field emissiondevice formed thereon are arranged such that the phosphor layer and thecold cathode field emission device face each other, and the substrateand the supporting member are bonded to each other in theircircumferential portions, the method including the steps of; (A) forminga cathode electrode on the supporting member, (B) forming an insulatinglayer on the supporting member and the cathode electrode, (C) forming agate electrode having an opening portion on the insulating layer, (D)forming a second opening portion through the insulating layer, saidsecond opening portion communicating with the opening portion formedthrough the gate electrode, thereby to expose the cathode electrode in abottom portion of the second opening portion, and (E) forming anelectron emitting portion on the cathode electrode exposed in the bottomportion of the second opening portion, whereby the cold cathode fieldemission device is formed, in which the electron emitting portioncomprises a carbon-group-material layer and afluoride-carbide-containing thin film formed on the surface of thecarbon-group-material layer, and the step of forming the electronemitting portion comprises the step of forming thefluoride-carbide-containing thin film on the surface of the formedcarbon-group-material layer from a fluorine-containing hydrocarbon gas.141. The manufacturing method of a cold cathode field emission displayaccording to claim 140, in which the carbon-group-material layer isformed from a hydrocarbon gas in the step of forming the electronemitting portion.
 142. The manufacturing method of a cold cathode fieldemission display according to claim 141, in which interposed between thestep (A) and the step (B) is the step of forming a selective-growthregion on the cathode electrode, an insulating layer is formed on thesupporting member, the selective-growth region and the cathode electrodein the step (B), a second opening portion is formed through theinsulating layer in the step (D), said second opening portioncommunicating with the opening portion formed through the gateelectrode, thereby to expose the selective-growth region in the bottomportion of the second opening portion, and the electron emitting portionis formed on the selective-growth region exposed in the bottom portionof the second opening portion in the step (E).
 143. The manufacturingmethod of a cold cathode field emission display according to claim 141,in which interposed between the step (D) and the step (E) is the step offorming a selective-growth region on the cathode electrode exposed inthe bottom portion of the second opening portion, and the electronemitting portion is formed on the selective-growth region in the step(E) in place of forming the electron emitting portion on the cathodeelectrode exposed in the bottom portion of the second opening portion.144. The manufacturing method of a cold cathode field emission displayaccording to claim 140, in which a dispersion of carbon nano-tubestructures in a binder material is applied onto the cathode electrodeand the binder material is fired or cured to form thecarbon-group-material layer in the step of forming the electron emittingportion.
 145. The manufacturing method of a cold cathode field emissiondisplay according to claim 140, in which a metal compound solution inwhich carbon nano-tube structures are dispersed is applied onto thecathode electrode and then the metal compound is fired, to form thecarbon-group-material layer in the step of forming the electron emittingportion.
 146. A manufacturing method of a cold cathode field emissiondisplay, in which a substrate having an anode electrode and a phosphorlayer formed thereon and a supporting member having a cold cathode fieldemission device formed thereon are arranged such that the phosphor layerand the cold cathode field emission device face each other, and thesubstrate and the supporting member are bonded to each other in theircircumferential portions, the method including the steps of; (A) forminga cathode electrode on the supporting member, (B) forming an insulatinglayer on the supporting member and the cathode electrode, (C) forming agate electrode having an opening portion on the insulating layer, (D)forming a second opening portion through the insulating layer, saidsecond opening portion communicating with the opening portion formedthrough the gate electrode, thereby to expose the cathode electrode in abottom portion of the second opening portion, and (E) forming anelectron emitting portion on the cathode electrode exposed in the bottomportion of the second opening portion, whereby the cold cathode fieldemission device is formed, in which the electron emitting portioncomprises a carbon-group-material layer, and the step of forming theelectron emitting portion comprises the step of terminating the surfaceof the formed carbon-group-material layer with a fluorine-containinghydrocarbon gas.
 147. The manufacturing method of a cold cathode fieldemission display according to claim 146, in which thecarbon-group-material layer is formed from a hydrocarbon gas in the stepof forming the electron emitting portion.
 148. The manufacturing methodof a cold cathode field emission display according to claim 147, inwhich interposed between the step (A) and the step (B) is the step offorming a selective-growth region on the cathode electrode, aninsulating layer is formed on the supporting member, theselective-growth region and the cathode electrode in the step (B), asecond opening portion is formed through the insulating layer in thestep (D), said second opening portion communicating with the openingportion formed through the gate electrode, thereby to expose theselective-growth region in the bottom portion of the second openingportion, and the electron emitting portion is formed on theselective-growth region exposed in the bottom portion of the secondopening portion in the step (E).
 149. The manufacturing method of a coldcathode field emission display according to claim 147, in whichinterposed between the step (D) and the step (E) is the step of forminga selective-growth region on the cathode electrode exposed in the bottomportion of the second opening portion, and the electron emitting portionis formed on the selective-growth region in the step (E) in place offorming the electron emitting portion on the cathode electrode exposedin the bottom portion of the second opening portion.
 150. Themanufacturing method of a cold cathode field emission display accordingto claim 146, in which a dispersion of carbon nano-tube structures in abinder material is applied onto the cathode electrode and the bindermaterial is fired or cured to form the carbon-group-material layer inthe step of forming the electron emitting portion.
 151. Themanufacturing method of a cold cathode field emission display accordingto claim 146, in which a metal compound solution in which carbonnano-tube structures are dispersed is applied onto the cathode electrodeand then the metal compound is fired, to form the carbon-group-materiallayer in the step of forming the electron emitting portion.
 152. Amanufacturing method of a cold cathode field emission display, in whicha substrate having an anode electrode and a phosphor layer formedthereon and a supporting member having a cold cathode field emissiondevice formed thereon are arranged such that the phosphor layer and thecold cathode field emission device face each other, and the substrateand the supporting member are bonded to each other in theircircumferential portions, the method including the steps of; (A) forminga cathode electrode on the supporting member, (B) forming an electronemitting portion on the cathode electrode, and (C) forming a gateelectrode having an opening portion above the electron emitting portion,whereby the cold cathode field emission device is formed, in which theelectron emitting portion comprises a carbon-group-material layer, andthe step of forming the electron emitting portion comprises the step offorming the carbon-group-material layer from a hydrocarbon gas and afluorine-containing hydrocarbon gas.
 153. The manufacturing method of acold cathode field emission display according to claim 152, in which thestep (B) is followed by forming an insulating layer on the entiresurface, and the step (C) is followed by forming a second openingportion through the insulating layer, said second opening portioncommunicating with the opening portion formed through the gateelectrode, thereby to expose the carbon-group-material layer in a bottomportion of the second opening portion.
 154. The manufacturing method ofa cold cathode field emission display according to claim 152, in whichinterposed between the step (A) and the step (B) is the step of forminga selective-growth region on the cathode electrode, and the electronemitting portion is formed on the selective-growth region in the step(B) in place of forming the electron emitting portion on the cathodeelectrode.
 155. A manufacturing method of a cold cathode field emissiondisplay, in which a substrate having an anode electrode and a phosphorlayer formed thereon and a supporting member having a cold cathode fieldemission device formed thereon are arranged such that the phosphor layerand the cold cathode field emission device face each other, and thesubstrate and the supporting member are bonded to each other in theircircumferential portions, the method including the steps of; (A) forminga cathode electrode on the supporting member, (B) forming an electronemitting portion on the cathode electrode, and (C) forming a gateelectrode having an opening portion above the electron emitting portion,whereby the cold cathode field emission device is formed, in which theelectron emitting portion comprises a carbon-group-material layer and afluoride-carbide-containing thin film formed on the surface of thecarbon-group-material layer, and the step of forming the electronemitting portion comprises the step of forming thefluoride-carbide-containing thin film on the surface of the formedcarbon-group-material layer from a fluorine-containing hydrocarbon gas.156. The manufacturing method of a cold cathode field emission displayaccording to claim 155, in which the step (B) is followed by forming aninsulating layer on the entire surface, and the step (C) is followed byforming a second opening portion through the insulating layer, saidsecond opening portion communicating with the opening portion formedthrough the gate electrode, thereby to expose the carbon-group-materiallayer in a bottom portion of the second opening portion.
 157. Themanufacturing method of a cold cathode field emission display accordingto claim 155, in which the carbon-group-material layer is formed from ahydrocarbon gas in the step of forming the electron emitting portion.158. The manufacturing method of a cold cathode field emission displayaccording to claim 157, in which interposed between the step (A) and thestep (B) is the step of forming a selective-growth region on the cathodeelectrode, and the electron emitting portion is formed on theselective-growth region in the step (B) in place of forming the electronemitting portion on the cathode electrode.
 159. The manufacturing methodof a cold cathode field emission display according to claim 155, inwhich a dispersion of carbon nano-tube structures in a binder materialis applied onto the cathode electrode and the binder material is firedor cured to form the carbon-group-material layer in the step of formingthe electron emitting portion.
 160. The manufacturing method of a coldcathode field emission display according to claim 155, in which a metalcompound solution in which carbon nano-tube structures are dispersed isapplied onto the cathode electrode and then the metal compound is fired,to form the carbon-group-material layer in the step of forming theelectron emitting portion.
 161. A manufacturing method of a cold cathodefield emission display, in which a substrate having an anode electrodeand a phosphor layer formed thereon and a supporting member having acold cathode field emission device formed thereon are arranged such thatthe phosphor layer and the cold cathode field emission device face eachother, and the substrate and the supporting member are bonded to eachother in their circumferential portions, the method including the stepsof; (A) forming a cathode electrode on the supporting member, (B)forming an electron emitting portion on the cathode electrode, and (C)forming a gate electrode having an opening portion above the electronemitting portion, whereby the cold cathode field emission device isformed, in which the electron emitting portion comprises acarbon-group-material layer, and the step of forming the electronemitting portion comprises the step of terminating the surface of theformed carbon-group-material layer with a fluorine-containinghydrocarbon gas.
 162. The manufacturing method of a cold cathode fieldemission display according to claim 161, in which the step (B) isfollowed by forming an insulating layer on the entire surface, and thestep (C) is followed by forming a second opening portion through theinsulating layer, said second opening portion communicating with theopening portion formed through the gate electrode, thereby to expose thecarbon-group-material layer in a bottom portion of the second openingportion.
 163. The manufacturing method of a cold cathode field emissiondisplay according to claim 161, in which the carbon-group-material layeris formed from a hydrocarbon gas in the step of forming the electronemitting portion.
 164. The manufacturing method of a cold cathode fieldemission display according to claim 163, in which interposed between thestep (A) and the step (B) is the step of forming a selective-growthregion on the cathode electrode, and the electron emitting portion isformed on the selective-growth region in the step (B) in place offorming the electron emitting portion on the cathode electrode.
 165. Themanufacturing method of a cold cathode field emission display accordingto claim 161, in which a dispersion of carbon nano-tube structures in abinder material is applied onto the cathode electrode and the bindermaterial is fired or cured to form the carbon-group-material layer inthe step of forming the electron emitting portion.
 166. Themanufacturing method of a cold cathode field emission display accordingto claim 161, in which a metal compound solution in which carbonnano-tube structures are dispersed is applied onto the cathode electrodeand then the metal compound is fired, to form the carbon-group-materiallayer in the step of forming the electron emitting portion.